Composition, shaped article production method, and shaped article

ABSTRACT

A composition according to the invention contains a cellulose derivative having a liquid crystalline functional group and a liquid crystalline solvent having a reactive functional group. The reactive functional group preferably contains a carbon-carbon double bond. The reactive functional group is preferably a (meth)acryloyl group.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to Japanese Patent Application No.2015-065908 filed on Mar. 27, 2015. The entire disclosures of JapanesePatent Application No. 2015-065908 is hereby incorporated herein byreference.

BACKGROUND

1. Technical Field

The present invention relates to a composition, a shaped articleproduction method, and a shaped article.

2. Related Art

Cellulose is a recyclable resource and is accumulated abundantly onearth, and also has excellent biocompatibility and degradability, andtherefore is an environmentally friendly material. Accordingly,cellulose has attracted attention recently, and its effectiveutilization has been demanded (see, for example, JP-A-7-268724).

However, in the past, cellulose was used in paper products such asprinting paper and corrugated cardboard in most cases, and other thanthese, it was merely used in fibers (cellulose fibers) and the like.Therefore, there was a problem that various advantageous characteristicsof cellulose are not fully utilized.

Further, cellulose has been known to be able to constitute a memberhaving excellent mechanical strength because of its chemical structure,however, it has not yet been applied on a practical level to a memberhaving high strength and high durability which sufficiently exhibits thecharacteristics of cellulose.

SUMMARY

An advantage of some aspects of the invention is to provide acomposition which can be favorably used for producing a shaped articlewhich contains a cellulosic material and has excellent strength, toprovide a shaped article which contains a cellulosic material and hasexcellent strength, and to provide a shaped article production methodcapable of efficiently producing a shaped article which contains acellulosic material and has excellent strength.

The advantage can be achieved by the invention describe below.

A composition according to an aspect of the invention contains acellulose derivative having a liquid crystalline functional group and aliquid crystalline solvent having a reactive functional group.

According to this configuration, a composition which can be favorablyused for producing a shaped article which contains a cellulosic materialand has excellent strength can be provided.

In the composition according to the aspect of the invention, it ispreferred that the reactive functional group contains a carbon-carbondouble bond.

According to this configuration, the productivity of the shaped articlecan be made more excellent. Further, the strength, durability, andreliability of the shaped article can be made more excellent.

In the composition according to the aspect of the invention, it ispreferred that the reactive functional group is a (meth)acryloyl group.

According to this configuration, the productivity of the shaped articlecan be made further more excellent. Further, the strength, durability,and reliability of the shaped article can be made further moreexcellent.

In the composition according to the aspect of the invention, it ispreferred that the cellulose derivative has the liquid crystallinefunctional group introduced into a repeating unit of a polymer chainhaving a repeating structure introduced into a cellulose backbonestructure.

According to this configuration, the mechanical strength, durability,and reliability of the shaped article can be made more excellent.

In the composition according to the aspect of the invention, it ispreferred that the cellulose derivative contains an ionic moiety as achemical structure in common with an ionic liquid.

According to this configuration, the formability when a shaped articlehaving a given shape is produced can be made more excellent, and thus,the dimensional accuracy of the shaped article to be produced can bemade more excellent. Further, the mechanical strength, durability, andthe like of the shaped article to be produced can be made moreexcellent. Further, the shaped article can be favorably applied to, forexample, a medical device, and the like.

In the composition according to the aspect of the invention, it ispreferred that the cellulose derivative has a block containing aplurality of ionic moieties and a block containing a plurality of liquidcrystalline functional groups.

According to this configuration, the dimensional accuracy, mechanicalstrength, and the like of the shaped article to be produced can be mademore excellent.

In the composition according to the aspect of the invention, it ispreferred that a chemical reaction involving the reactive functionalgroup of the liquid crystalline solvent proceeds by UV irradiation.

According to this configuration, the productivity of the shaped articlecan be made more excellent while more effectively preventing undesirabledenaturation, deterioration, or the like of the materials. Further, thestructure of a production apparatus for the shaped article can beprevented from being complicated, and thus, the production cost of theshaped article can be kept low.

A shaped article production method according to an aspect of theinvention includes supplying the composition according to the aspect ofthe invention, and allowing a chemical reaction involving the reactivefunctional group of the liquid crystalline solvent to proceed.

According to this configuration, a shaped article production methodcapable of efficiently producing a shaped article which contains acellulosic material and has excellent strength can be provided.

A shaped article production method according to an aspect of theinvention is a method for producing a three-dimensional shaped articleby performing a layer forming step of forming a layer using acomposition a plurality of times and stacking the layers, and includesapplying the composition according to the aspect of the invention to aregion where the three-dimensional shaped article is to be formed, andallowing a chemical reaction involving the reactive functional group ofthe liquid crystalline solvent to proceed.

According to this configuration, a shaped article production methodcapable of efficiently producing a shaped article which contains acellulosic material and has excellent strength can be provided. Further,even a shaped article required to have high dimensional accuracy or ashaped article having a complicated shape can be efficiently producedwith sufficient dimensional accuracy. Further, the production method canbe favorably applied also to the production of a plurality of types ofshaped articles having different shapes and sizes.

In the shaped article production method according to the aspect of theinvention, it is preferred that the application of the composition isperformed by an inkjet method.

According to this configuration, the dimensional accuracy of the shapedarticle can be further increased.

In the shaped article production method according to the aspect of theinvention, it is preferred that when the composition is applied to aregion where the three-dimensional shaped article is to be formed, thecellulose derivative is in a dissolved state in the liquid crystallinesolvent in the composition.

According to this configuration, the liquid crystalline solvent and thecellulose derivative contained in the composition can be more favorablyaligned, and thus, the mechanical strength of the shaped article to beobtained finally can be made more excellent.

In the shaped article production method according to the aspect of theinvention, it is preferred that the composition is applied onto a memberhaving been subjected to an alignment treatment.

According to this configuration, the mechanical strength, durability,reliability, and the like of the shaped article to be obtained finallycan be made more excellent.

A shaped article according to an aspect of the invention is producedusing the composition according to the aspect of the invention.

According to this configuration, a shaped article which contains acellulosic material and has excellent strength can be provided.

A shaped article according to an aspect of the invention is producedusing the production method according to the aspect of the invention.

According to this configuration, a shaped article which contains acellulosic material and has excellent strength can be provided.

It is preferred that the shaped article according to the aspect of theinvention is a stent.

A stent is held in a state of being inserted into the body for a longperiod of time, and is required to have excellent strength, durability,biocompatibility, and the like. However, according to the invention,these requirements can be satisfied. Accordingly, when the invention isapplied to a stent, the effect of the invention can be more remarkablyexhibited.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be described with reference to the accompanyingdrawings, wherein like numbers reference like elements.

FIGS. 1A to 1H show cross-sectional views schematically illustratingrespective steps in a first embodiment of a shaped article productionmethod according to the invention.

FIGS. 2A to 2F show cross-sectional views schematically illustratingrespective steps in a second embodiment of a shaped article productionmethod according to the invention.

FIG. 3 is a cross-sectional view schematically showing a firstembodiment of a production apparatus to be used for producing a shapedarticle according to the invention.

FIG. 4 is a cross-sectional view schematically showing a secondembodiment of a production apparatus to be used for producing a shapedarticle according to the invention.

FIG. 5 is a perspective view showing the shape of a three-dimensionalshaped article (three-dimensional shaped article A) produced in each ofExamples and Comparative Examples.

FIG. 6 is a perspective view showing the shape of a three-dimensionalshaped article (three-dimensional shaped article B) produced in each ofExamples and Comparative Examples.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

Hereinafter, preferred embodiments of the invention will be described indetail with reference to the accompanying drawings.

Composition

First, a composition according to the invention will be described indetail.

The composition according to the invention is used for producing ashaped article, and contains a cellulose derivative having a liquidcrystalline functional group and a liquid crystalline solvent having areactive functional group.

According to this, a member (shaped article) to be produced using thecomposition can be made to have excellent strength and the like whilehaving the advantageous characteristics of cellulose.

More specifically, since both of the cellulose derivative and the liquidcrystalline solvent have a liquid crystalline moiety, the constituentmaterials can be favorably aligned in a shaped article to be producedusing the composition. According to this, the intermolecular interaction(intermolecular force) or the like of the constituent materials in theshaped article can be increased. Then, by allowing a chemical reactioninvolving the reactive functional group of the liquid crystallinesolvent to proceed in this state, the liquid crystalline solvent issolidified (cured) in a state where the moiety having liquidcrystallinity is aligned. Accordingly, the mechanical strength,durability, reliability, and the like of the shaped article to beobtained can be made excellent.

Further, by using a solvent having liquid crystallinity as the solvent,the affinity and solubility of the cellulose derivative having a liquidcrystalline functional group for the liquid crystalline solvent can beincreased. According to this, the fluidity of the composition whenproducing the shaped article can be made sufficiently high, and the easeof handling (handleability) of the composition can be made excellent,and thus, the production of the shaped article can be favorablyperformed. In particular, even in the case where the content of thecellulose derivative in the composition is set high, the fluidity of thecomposition can be made sufficiently excellent, and therefore, a shapedarticle having a high density can be favorably produced, and thestrength and the like of the shaped article can be further improved.Further, by including the liquid crystalline solvent, it is notnecessary to use a volatile solvent other than the liquid crystallinesolvent, and even if a volatile solvent is used, the content thereof canbe set low, and therefore, deformation (shrinkage or the like)accompanying the removal of the solvent can be prevented and suppressed,and thus, the dimensional accuracy of the shaped article can be madeexcellent.

Hereinafter, components constituting the composition according to theinvention will be described.

Cellulose Derivative

Cellulose is a compound in which β-glucose is polymerized through aglycoside bond, however, in the invention, the cellulose derivativemaybe any as long as it is a compound which can be derived fromcellulose by a chemical reaction, and examples thereof include acellulose derivative obtained by substituting at least part of thehydroxy groups of cellulose with another substituent (including acellulose derivative obtained by a condensation reaction of at leastpart of the hydroxy groups of cellulose with another compound, etc.).

The substituent may be introduced into all the repeating units (glucosestructures) in the same manner, or maybe introduced into only part ofthe repeating units (glucose structures). Further, the position wherethe substituent is introduced may be different among the repeating units(glucose structures).

The cellulose derivative contained in the composition according to theinvention may be any as long as it has a functional group having liquidcrystallinity (liquid crystalline functional group).

Examples of the functional group (atomic group) having liquidcrystallinity include groups represented by the following formulae (6).

The liquid crystalline functional group may be introduced into anyposition of the cellulose derivative, but is preferably introduced intoa hydroxy group bonded to the carbon atom at position 6 of β-glucoseconstituting cellulose by a chemical reaction. That is, it is preferredthat the liquid crystalline functional group is introduced into R³ inthe following formula (2).

In the formula (2), R¹, R², R³, R⁴, and R⁵ each independently representa hydrogen atom or a substituent, provided that at least one functionalgroup is introduced into the molecule.

According to this, the effect of the liquid crystalline functional groupon the alignment of the cellulose derivative can be more remarkablyexhibited, and thus, the strength, durability, and reliability of theshaped article can be made more excellent. Further, the synthesis of thecellulose derivative as the constituent component of the composition canbe efficiently performed. As a result, this configuration can alsocontribute to the reduction of the production cost of the shapedarticle.

At least one liquid crystalline functional group may be introduced intothe molecule of the cellulose derivative, however, it is preferred thata plurality of liquid crystalline functional groups are introduced intothe molecule of the cellulose derivative.

According to this, the cellulose derivatives can be more favorablyarranged in the shaped article, and thus, the mechanical strength,durability, and reliability of the shaped article can be made moreexcellent.

In particular, it is preferred that a plurality of liquid crystallinefunctional groups are introduced into a repeating unit of a polymerchain (side chain) having a repeating structure introduced into acellulose backbone structure (basic structure).

According to this, for example, in the cellulose derivative molecule,the liquid crystalline functional groups can be more reliably made to beregularly present. Further, the conditions for a plurality of liquidcrystalline functional groups of the cellulose derivative molecule canbe favorably aligned. As a result, the cellulose derivative can be madeto be present at a high density in the shaped article, and thus, themechanical strength, durability, and reliability of the shaped articlecan be made more excellent.

Specific examples of a preferred cellulose derivative satisfying suchconditions include cellulose derivatives represented by the followingformulae (7) and (8).

In the formulae (7) and (8), n is an integer of 2 or more, 1 and m areeach independently an integer of 1 or more, R^(l), R², R⁴, and R⁵ areeach independently a hydrogen atom (H) or an acetyl group (CH₃CO), andR⁶ is an alkyl group.

The cellulose derivative contained in the composition may be any as longas it has a liquid crystalline functional group, but may have an ionicmoiety as a chemical structure in common with the ionic liquid.

The ionic liquid is a salt present in a liquid state and generally hasan ionic size (the size of an atomic group functioning as an ion) largerthan that of a normal salt in the form of a solid. By including theionic moiety as a chemical structure in common with such an ionicliquid, the cellulose derivative is more easily dissolved in a solvent.As a result, the cellulose derivative is dissolved in a solvent at ahigher concentration and more uniformly, so that the formability whenproducing a shaped article having a given shape can be made moreexcellent, and thus, the dimensional accuracy of the shaped article tobe produced can be made more excellent. Further, the cellulosederivative containing an ionic moiety also has a large intermolecularbinding force, and therefore, the mechanical strength, durability, andthe like of the shaped article to be produced can be made moreexcellent. Further, the hydrophilicity of the shaped article can be mademore excellent, and for example, the shaped article can be favorablyapplied to a medical device or the like.

Examples of a cation constituting the ionic liquid include variouscations such as imidazole-based, pyridine-based, alicyclic amine-based,and aliphatic amine-based cations.

Examples of an anion constituting the ionic liquid include variousanions such as halogen-based anions (such as bromide anions and triflateanions), boron-based anions (such as tetraphenyl borate anions), andphosphorus-based anions (such as hexafluorophosphate anions).

Specific examples of the ionic liquid includeN-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide,1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide,1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide,dimethylpropylimidazolium iodide, butylmethylimidazolium iodide,1,2-dimethyl-3-n-propylimidazolium iodide, 1-methyl-3-n-hexylimidazoliumiodide, 1,2-dimethyl-3-ethylimidazolium trifluoromethanesulfonate,1-methyl-3-butylimidazolium nonafluorobutylsulfonate,1-methyl-3-ethylimidazolium bis(trifluoromethyl)sulfonylimide,1-methyl-3-n-hexylimidazolium bis(trifluoromethyl)sulfonylimide,1-methyl-3-n-hexylimidazolium dicyanamide, lithiumbisfluorosulfonylimide (LiFSI), lithiumbis(trifluoromethanesulfonyl)imide (LiTFSI),1-methyl-3-propylimidazolium bis(trifluorosulfonyl)imide,1-ethyl-3-butylimidazolium tetrafluoroborate, and1-hexyl-3-methylimidazolium hexafluorophosphate.

In particular, the ionic moiety of the cellulose derivative preferablyhas an imidazolium salt structure.

According to this, the effect of having the ionic moiety as describedabove is more remarkably exhibited.

Examples of the ionic moiety include a moiety represented by thefollowing formula (3).

In the formula (3), R⁷ is a hydrogen atom (H) or an alkyl group.

The ionic moiety may be introduced into any position of the cellulosederivative, but is preferably introduced into a hydroxy group bonded tothe carbon atom at position 6 of β-glucose constituting cellulose by achemical reaction. That is, it is preferred that the ionic moiety isintroduced into R³ in the following formula (2).

In the formula (2), R¹, R², R³, R⁴, and R⁵ each independently representa hydrogen atom or a substituent, provided that at least one functionalgroup including the ionic moiety is introduced into the molecule.

According to this, the ionic moiety can be efficiently exposed to theoutside of the molecule of the cellulose derivative, and the effect asdescribed above can be more remarkably exhibited. Further, the synthesisof the cellulose derivative as the constituent component of thecomposition can be efficiently performed. As a result, thisconfiguration can also contribute to the reduction of the productioncost of the shaped article.

It is preferred that a plurality of ionic moieties are introduced intothe molecule of the cellulose derivative.

According to this, the effect of having the ionic moiety as describedabove is more remarkably exhibited.

In particular, it is preferred that a plurality of ionic moieties areintroduced into a repeating unit of a polymer chain (side chain) havinga repeating structure introduced into a cellulose backbone structure(basic structure).

According to this, the effect of having the ionic moiety as describedabove is more remarkably exhibited. Further, the synthesis of thecellulose derivative as the constituent component of the composition canbe efficiently performed. As a result, this configuration can alsocontribute to the reduction of the production cost of the shapedarticle.

Specific examples of a preferred cellulose derivative satisfying suchconditions include a cellulose derivative represented by the followingformula (17).

In the formula (17), n and m are each independently an integer of 2 ormore, 1 is an integer of 1 or more, R¹, R², R⁴, and R⁵ are eachindependently a hydrogen atom (H) or an acetyl group (CH₃CO), and R⁷ isa hydrogen atom (H) or an alkyl group.

It is preferred that the cellulose derivative has the liquid crystallinefunctional groups and the ionic moieties in the form of blocks,respectively. In other words, it is preferred that the cellulosederivative has a block containing a plurality of liquid crystallinefunctional groups and a block containing a plurality of ionic moieties.

According to this, both of the effect of having a plurality of liquidcrystalline functional groups and the effect of having a plurality ofionic moieties can be more remarkably exhibited, and thus, thedimensional accuracy, mechanical strength, and the like of the shapedarticle to be produced can be made more excellent.

Specific examples of a preferred cellulose derivative satisfying suchconditions include a cellulose derivative represented by the followingformula (18).

In the formula (18), l, m, and n are each independently an integer of 2or more, R¹, R², R⁴, and R⁵ are each independently a hydrogen atom (H)or an acetyl group (CH₃CO), R⁸ is a group represented by the followingformula (9), and R⁹ is a group represented by the following formula (10)or (11).

In the formula (9), k is an integer of 1 or more, and R⁷ is a hydrogenatom (H) or an alkyl group.

In the formulae (10) and (11), j is an integer of 1 or more, and R⁶ is ahydrogen atom (H) or an alkyl group.

Further, the cellulose derivative may have a functional group (reactivefunctional group) which binds the molecular chains of the cellulosederivative through a covalent bond.

In this manner, by binding the molecules of the cellulose derivativethrough a covalent bond, the advantageous characteristics (for example,high strength, light weight, biosafety, environmental safety, etc.)intrinsic to the cellulosic material can be more effectively exhibitedwhile effectively preventing a decrease in the strength or the like dueto separation or the like between the molecules. Further, the mechanicalstrength, durability, and reliability of the shaped article to beobtained finally can be made more excellent. Further, for example, byinterlacing a molecular chain formed by a chemical reaction involvingthe reactive functional group of the liquid crystalline solvent (whichwill be described in detail later) with a molecular chain formed by areaction between the cellulose derivatives, the mechanical strength,durability, and the like of the shaped article to be obtained finallycan be made further more excellent.

Such a functional group (reactive functional group) of the cellulosederivative may be a group which directly binds the molecules of thecellulose derivative or may be a group which binds the molecules of thecellulose derivative through another atom (at least one atom). Morespecifically, for example, the functional group of the cellulosederivative may be a group which reacts with the reactive functionalgroup of the liquid crystalline solvent.

Examples of the functional group (reactive functional group) include agroup containing a carbon-carbon double bond, a hydroxy group, and acarboxyl group, however, a group containing a carbon-carbon double bondis preferred.

According to this, the reactivity of the cellulose derivative can bemade excellent, and the productivity of the shaped article to beproduced using the composition according to the invention can be mademore excellent. In addition, the unreacted cellulose derivative can beeffectively prevented from being undesirably contained much in theshaped article to be produced. Further, the chemical stability of thecovalent bond to be formed by the reaction can be made more excellent.As a result, the strength, durability, and reliability of the shapedarticle can be made more excellent. Further, the range of choice of acompound which reacts with the cellulose derivative (a compound whichcan react with the reactive functional group of the cellulosederivative) is expanded, and thus, the range of design of the shapedarticle is expanded.

Examples of the functional group (reactive functional group) containinga carbon-carbon double bond include a vinyl group and a (meth) acryloylgroup, however, a (meth) acryloyl group is preferred.

According to this, the reactivity of the cellulose derivative can bemade further more excellent, and thus, the productivity of the shapedarticle can be made further more excellent. In addition, the unreactedcellulose derivative can be more effectively prevented from beingundesirably contained much in the final shaped article. Further, thechemical stability of the covalent bond to be formed by the reaction canbe made more excellent. As a result, the strength, durability, andreliability of the shaped article can be made further more excellent.Further, the range of choice of a compound which reacts with thecellulose derivative (a compound which can react with the reactivefunctional group of the cellulose derivative) is expanded, and thus, therange of design of the shaped article is expanded.

The reactive functional group may be introduced into any position of thecellulose derivative, but is preferably introduced into a side chain ofthe cellulose derivative different from the cellulose backbone structure(basic backbone structure).

According to this, the effect of having the reactive functional groupcan be exhibited while more effectively exhibiting the advantageouscharacteristics (for example, high strength, light weight, biosafety,environmental safety, etc.) intrinsic to cellulose. Further, the sidechain of the cellulose derivative generally has higher reactivity thanthe cellulose backbone structure (basic backbone structure), andtherefore, the reaction involving the reactive functional group can beallowed to proceed more efficiently.

In particular, the reactive functional group is preferably introducedinto a hydroxy group bonded to the carbon atom at position 6 ofβ-glucose constituting cellulose by a chemical reaction. That is, it ispreferred that the reactive functional group is introduced into R³ inthe above formula (2).

According to this, the steric hindrance of the reactive functional groupcan be made small, or the like, and thus, the reactivity of thecellulose derivative can be made excellent, and thus, the productivityof the shaped article can be made more excellent. In addition, theunreacted cellulose derivative can be prevented from being undesirablycontained much in the final shaped article. Accordingly, the strength,durability, and reliability of the shaped article can be made moreexcellent. Further, the synthesis of the cellulose derivative as theconstituent component of the composition can be efficiently performed.As a result, this configuration can also contribute to the reduction ofthe production cost of the shaped article.

Further, the reactive functional group is preferably introduced into thecellulose backbone through at least one carbon-carbon single bond in thebasic cellulose structure.

According to this, the reactivity of the reactive functional group canbe made more excellent, and thus, the productivity and the like of theshaped article can be made more excellent.

Specific examples of a preferred cellulose derivative satisfying theconditions as described above include cellulose derivatives representedby the following formulae (12), (13), and (14).

In the formulae (12), (13), and (14), l, m, and n are each independentlyan integer of 2 or more, q and r are each independently an integer of 1or more, R¹, R², R⁴, and R⁵ are each independently a hydrogen atom (H)or an acetyl group (CH₃CO), and R⁸ is a group represented by the aboveformula (9).

When the cellulose derivative is a cellulose derivative represented byany of the formulae (12) to (14), the effect as described above is moreremarkably exhibited.

It is preferred that the reaction to bond the molecular chains of thecellulose derivative through a covalent bond proceeds by UV irradiation.

According to this, the productivity of the shaped article can be mademore excellent while more effectively preventing undesirabledenaturation, deterioration, or the like of the materials. Further, thestructure of the production apparatus for the shaped article can beprevented from being complicated, and thus, the production cost of theshaped article can be kept low.

It is preferred that the cellulose derivative (particularly, thecellulose derivative in which the reactive functional group contains acarbon-carbon double bond) reacts with a siloxane compound having two ormore Si—H bonds in the molecule.

According to this, the efficiency of the formation of the covalent bondcan be made more excellent, and thus, the productivity of the shapedarticle can be made more excellent. In addition, the unreacted cellulosederivative can be effectively prevented from being undesirably containedmuch in the shaped article. Further, the chemical stability of thecovalent bond to be formed by the reaction can be made more excellent.As a result, the strength, durability, and reliability of the shapedarticle can be made more excellent. Further, the chemical reaction toform the covalent bond by heating can be favorably performed.

The siloxane compound with which the cellulose derivative reactspreferably has two or more Si—H bonds in the molecule, but morepreferably has three or more Si—H bonds in the molecule.

According to this, a more complicated net structure can be formed by thechemical reaction to form the covalent bond, and thus, the strength,durability, and the like of the shaped article can be made moreexcellent.

The siloxane compound with which the cellulose derivative reacts may bea chain compound, but is preferably a cyclic compound.

According to this, the strength, durability, and the like of the shapedarticle can be made more excellent.

Examples of the siloxane compound (the siloxane compound which reactswith the cellulose derivative) satisfying such conditions include asiloxane compound represented by the following formula (4).

The cellulose derivative (particularly, the cellulose derivative inwhich the reactive functional group contains a carbon-carbon doublebond) may be a cellulose derivative which reacts with a crosslinkingagent.

According to this, for example, a more complicated net structure can beformed by the chemical reaction to form the covalent bond, and thus, thestrength, durability, and the like of the shaped article can be mademore excellent. Further, for example, by irradiation with a light suchas a UV light, the chemical reaction to form the covalent bond can befavorably performed.

Examples of the crosslinking agent include compounds having apolymerizable functional group such as a vinyl group or a (meth)acryloylgroup.

Among these, as the crosslinking agent, a compound having a plurality ofpolymerizable functional groups in the molecule is preferred, and acompound in which an alkyl chain is modified with a polymerizablefunctional group at both ends is more preferred.

Examples of such a crosslinking agent include a compound represented bythe following formula (5).

In the formula (5), n is an integer of 1 or more.

The weight average molecular weight of the cellulose derivativecontained in the composition according to the invention is notparticularly limited, but is preferably 5, 000 or more and 10,000,000 orless, more preferably 10,000 or more and 7,000,000 or less.

According to this, the strength, durability, and reliability of theshaped article to be produced can be made more excellent. Further, thestorage stability, the ease of handling (for example, the ejectionstability by an inkjet method), and the like of the composition can bemade excellent.

The content of the cellulose derivative in the composition according tothe invention is not particularly limited, but is preferably 30% by massor more and 95% by mass or less, more preferably 40% by mass or more and90% by mass or less, further more preferably 45% by mass or more and 85%by mass or less.

According to this, the storage stability, the ease of handling (forexample, the ejection stability by an inkjet method), and the like ofthe composition can be made more excellent, and also in the shapedarticle to be produced using the composition, the advantageouscharacteristics of the cellulosic material can be more effectivelyexhibited, and thus, the strength, durability, reliability, and the likeof the shaped article can be made more excellent.

The form of the cellulose derivative in the composition is notparticularly limited, and the cellulose derivative maybe in a dissolvedstate in the liquid crystalline solvent, or may be in a dispersed statetherein, or may be in a mixed state of these states.

In the case where the cellulose derivative is dispersed in thecomposition, the average particle diameter of the cellulose derivativein the composition is not particularly limited, but is preferably 5.0 μmor less, more preferably 1.0 μm or less.

According to this, the strength, durability, reliability, and the likeof the shaped article to be produced can be made more excellent whilemaking the storage stability, the ease of handling (for example, theejection stability by an inkjet method), and the like of the compositionexcellent.

The “average particle diameter” as used herein refers to an averageparticle diameter on a volume basis and can be determined by, forexample, adding a sample to methanol, followed by dispersion for 3minutes using an ultrasonic disperser, and then, measuring the resultingdispersion liquid using a particle size distribution analyzer employinga Coulter counter method (for example, model TA-II, manufactured byCoulter Electronics, Inc., or the like) with an aperture of 50 μm.

Liquid Crystalline Solvent

As described above, the composition according to the invention containsa liquid crystalline solvent having a reactive functional group inaddition to the cellulose derivative having a liquid crystallinefunctional group.

According to this, the above-mentioned cellulose derivative can befavorably dissolved or dispersed in the composition, and the effect asdescribed above can be reliably exhibited.

The liquid crystalline solvent contains a liquid crystalline moiety(liquid crystalline functional group).

Examples of the liquid crystalline functional group (atomic group)contained in the liquid crystalline solvent include groups representedby the above formulae (6).

The liquid crystalline functional group of the cellulose derivative andthe liquid crystalline functional group of the liquid crystallinesolvent may be the same or different, but are preferably the same.According to this, the affinity between the cellulose derivative and theliquid crystalline solvent can be made more excellent, and the effect asdescribed above is more remarkably exhibited.

The liquid crystalline solvent has a reactive functional group inaddition to a liquid crystalline functional group.

The reactive functional group of the liquid crystalline solvent is afunctional group contributing to the chemical reaction to form thecovalent bond.

Examples of the reactive functional group of the liquid crystallinesolvent include a group containing a carbon-carbon double bond, ahydroxy group, and a carboxyl group, however, a group containing acarbon-carbon double bond is preferred.

According to this, the reactivity of the liquid crystalline solvent canbe made excellent, and the productivity of the shaped article can bemade more excellent. In addition, the unreacted liquid crystallinesolvent can be effectively prevented from being undesirably contained inthe shaped article to be produced. Further, the chemical stability ofthe covalent bond to be formed by the reaction can be made moreexcellent. As a result, the strength, durability, and reliability of theshaped article can be made more excellent. Further, the range of choiceof a compound which reacts with the liquid crystalline solvent (acompound which can react with the reactive functional group of theliquid crystalline solvent) is expanded, and thus, the range of designof the liquid crystalline solvent is expanded.

Examples of the functional group (reactive functional group) containinga carbon-carbon double bond include a vinyl group and a (meth)acryloylgroup, however, a (meth)acryloyl group is preferred.

According to this, the reactivity of the liquid crystalline solvent canbe made further more excellent, and thus, the productivity of the shapedarticle can be made further more excellent. In addition, the unreactedliquid crystalline solvent can be more effectively prevented from beingundesirably contained in the final shaped article. Further, the chemicalstability of the covalent bond to be formed by the reaction can be mademore excellent. As a result, the strength, durability, and reliabilityof the shaped article can be made further more excellent. Further, therange of choice of a compound which reacts with the liquid crystallinesolvent (a compound which can react with the reactive functional groupof the liquid crystalline solvent) is expanded, and thus, the range ofdesign of the liquid crystalline solvent is further expanded.

Specific examples of a preferred liquid crystalline solvent satisfyingthe conditions as described above include solvents represented by thefollowing formulae (15) and (16).

In the formula (15), j is an integer of 1 or more, R¹ is a hydrogen atom(H) or a methyl group, and R⁶ is a hydrogen atom (H) or an alkyl group.

In the formula (16), j is an integer of 1 or more, and R¹ is a hydrogenatom (H) or a methyl group.

When the liquid crystalline solvent is a solvent represented by theformula (15) or (16), the effect as described above is more remarkablyexhibited.

The liquid crystalline solvent maybe a solvent which reacts with asiloxane compound having two or more Si—H bonds in the molecule asdescribed above or the like.

According to this, the same effect as described above is obtained.

It is preferred that the chemical reaction involving the reactivefunctional group of the liquid crystalline solvent proceeds by UVirradiation.

According to this, the productivity of the shaped article can be mademore excellent while more effectively preventing undesirabledenaturation, deterioration, or the like of the materials. Further, thestructure of the production apparatus for the shaped article can beprevented from being complicated, and thus, the production cost of theshaped article can be kept low.

The liquid crystalline solvent may at least partially react with thecellulose derivative to form a covalent bond with the cellulosederivative.

The content of the liquid crystalline solvent in the composition is notparticularly limited, but is preferably 5% by mass or more and 60% bymass or less, more preferably 10% by mass or more and 55% by mass orless, further more preferably 15% by mass or more and 50% by mass orless.

According to this, for example, the ejection stability and the like ofthe composition can be made more excellent, and also the mechanicalstrength and the like can be made more excellent while more effectivelyexhibiting the advantageous characteristics of the cellulosic materialin the shaped article.

When the content of the liquid crystalline solvent in the composition isrepresented by X_(s) (mass o) and the content of the cellulosederivative in the composition is represented by X_(c) (mass %), thecomposition preferably satisfies the following relationship:1≦X_(c)/X_(s)≦10, more preferably satisfies the following relationship:1.3≦X_(c)/X_(s)≦7, further more preferably satisfies the followingrelationship: 1.5≦X_(c)/X_(s)≦5.

By satisfying such a relationship, the dimensional accuracy, mechanicalstrength, durability, reliability, and the like of the shaped article tobe produced using the composition can be made more excellent while moreeffectively exhibiting the advantageous characteristics intrinsic to thecellulose derivative.

Other Component

The composition may contain a component (another component) other thanthe above-mentioned components. Examples of such a component includevarious coloring agents such as a pigment and a dye, various fluorescentmaterials, various light storage materials, various phosphorescentmaterials, an infrared absorbing material, a dispersant, a surfactant, acurable resin other than the liquid crystalline solvent, apolymerization initiator, a polymerization accelerator, a crosslinkingagent, a siloxane compound, a solvent other than the liquid crystallinesolvent (particularly, a polar solvent such as water or an ionicliquid), a cellulose derivative other than the above-mentioned cellulosederivative having a liquid crystalline functional group or cellulosewhich is not chemically modified, a permeation accelerator, a wettingagent (humectant), a fixing agent, an antifungal agent, a preservative,an antioxidant, a UV absorber, a chelating agent, a pH adjusting agent,a thickening agent, a filler, an anti-aggregation agent, and a defoamingagent.

By including a coloring agent in the composition, the shaped articlecolored in a color corresponding to the color of the coloring agent canbe obtained.

In particular, by including a pigment as the coloring agent, the lightresistance of the composition and the shaped article can be madefavorable. As the pigment, either of an inorganic pigment and an organicpigment can be used.

Examples of the inorganic pigment include carbon blacks (C.I. PigmentBlack 7) such as Furnace Black, Lamp Black, Acetylene Black, and ChannelBlack, iron oxide, and titanium oxide, and one pigment or a combinationof two or more pigments selected from these can be used.

Among the inorganic pigments described above, in order to take on apreferred white color, titanium oxide is preferred.

Examples of the organic pigment include azo pigments such as insolubleazo pigments, condensed azo pigments, azo lakes, and chelate azopigments, polycyclic pigments such as phthalocyanine pigments, peryleneand perinone pigments, anthraquinone pigments, quinacridone pigments,dioxane pigments, thioindigo pigments, isoindolinone pigments, andquinophthalone pigments, dye chelates (for example, basic dye typechelates, acidic dye type chelates, etc.), dye lakes (basic dye typelakes and acidic dye type lakes), nitro pigments, nitroso pigments,aniline black, and daylight fluorescent pigments, and one pigment or acombination of two or more pigments selected from these can be used.

Examples of a white pigment include C.I. Pigment White 6, 18, and 21.

Examples of a yellow pigment include C.I. Pigment Yellow 1, 2, 3, 4, 5,6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74,75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120,124, 128, 129, 133, 138, 139, 147, 151, 153, 154, 167, 172, and 180.

Examples of a magenta pigment include C.I. Pigment Red 1, 2, 3, 4, 5, 6,7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37,38, 40, 41, 42, 48 (Ca), 48 (Mn), 57 (Ca), 57:1, 88, 112, 114, 122, 123,144, 146, 149, 150, 166, 168, 170, 171, 175, 176, 177, 178, 179, 184,185, 187, 202, 209, 219, 224, and 245, and C.I. Pigment Violet 19, 23,32, 33, 36, 38, 43, and 50.

Examples of a cyan pigment include C.I. Pigment Blue 1, 2, 3, 15, 15:1,15:2, 15:3, 15:34, 15:4, 16, 18, 22, 25, 60, 65, and 66, and C.I. VatBlue 4 and 60.

Examples of the pigment other than the above-mentioned pigments includeC.I. Pigment Green 7 and 10, C.I. Pigment Brown 3, 5, 25, and 26, andC.I. Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43,and 63.

In the case where the composition contains a pigment, the averageparticle diameter of the pigment is preferably 300 nm or less, morepreferably 50 nm or more and 250 nm or less. According to this, forexample, the dispersion stability of the pigment in the composition andthe ejection stability of the composition can be made more excellent,and also an image with a higher image quality can be formed.

The “average particle diameter” as used herein refers to an averageparticle diameter on a volume basis and can be determined by, forexample, adding a sample to methanol, followed by dispersion for 3minutes using an ultrasonic disperser, and then, measuring the resultingdispersion liquid using a particle size distribution analyzer employinga Coulter counter method (for example, model TA-II, manufactured byCoulter Electronics, Inc., or the like) with an aperture of 50 μm.

Examples of the dye include acidic dyes, direct dyes, reactive dyes, andbasic dyes, and one dye or a combination of two or more dyes selectedfrom these can be used.

Examples of the fluorescent material constituting the compositioninclude C.I. Direct Yellow 87, C.I. Acid Red 52, C.I. Acid Red 92,Brilliant Sulfo Flavin, Eosin, Basic Flavin, Acridine Orange, Rhodamine6G, and Rhodamine B.

Examples of the light storage material constituting the compositioninclude sulfides of alkaline earth metals such as zinc, calcium,strontium, and barium, and light storage materials such as strontiumaluminate, or inorganic fluorescent materials such as various sulfidesand oxides exemplified by zinc sulfide and the like.

Examples of the phosphorescent material constituting the compositioninclude an iridium complex and a cyclometallated complex.

Examples of the infrared absorbing material constituting the compositioninclude ITO and ATO fine particles.

In the case where the composition contains a dispersoid such as apigment, if the composition further contains a dispersant, thedispersibility of the dispersoid can be made more favorable.

The dispersant is not particularly limited, but examples thereof includedispersants which are commonly used for preparing a pigment dispersionliquid such as a polymeric dispersant.

Specific examples of the polymeric dispersant include dispersantscontaining, as amain component, at least one of polyoxyalkylenepolyalkylene polyamine, a vinyl-based polymer or copolymer, an acrylicpolymer or copolymer, polyester, polyamide, polyimide, polyurethane, anamino-based polymer, a silicon-containing polymer, a sulfur-containingpolymer, a fluorine-containing polymer, and an epoxy resin.

When the composition contains a surfactant, the abrasion resistance ofthe shaped article can be made more favorable.

The surfactant is not particularly limited, however, for example, apolyester-modified silicone, a polyether-modified silicone, or the likeas a silicone-based surfactant can be used, and in particular, it ispreferred to use polyether-modified polydimethylsiloxane orpolyester-modified polydimethylsiloxane.

Examples of the curable resin include a thermosetting resin; variousphotocurable resins such as a visible light curable resin which is curedby a light in the visible light range (a photocurable resin in a narrowsense), a UV curable resin, and an IR curable resin; and an X-raycurable resin, and one curable resin or a combination of two or morecurable resins selected from these can be used.

As the UV curable resin (polymerizable compound), a compound whoseaddition polymerization or ring-opening polymerization is initiated by aradical species, a cationic species, or the like generated from aphotopolymerization initiator by UV irradiation, thereby forming apolymer is preferably used. Examples of the polymerization form of theaddition polymerization include radical, cationic, anionic, metathesis,and coordination polymerization. Further, examples of the polymerizationform of the ring-opening polymerization include cationic, anionic,radical, metathesis, and coordination polymerization.

Examples of an addition polymerizable compound include compounds havingat least one ethylenically unsaturated double bond. As the additionpolymerizable compound, a compound having at least one, preferably twoor more terminal ethylenically unsaturated bonds can be preferably used.

An ethylenically unsaturated polymerizable compound has a chemical formof a monofunctional polymerizable compound, a polyfunctionalpolymerizable compound, or a mixture thereof .

Examples of the monofunctional polymerizable compound includeunsaturated carboxylic acids (for example, acrylic acid, methacrylicacid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.)and esters thereof, and amides thereof.

As the polyfunctional polymerizable compound, an ester of an unsaturatedcarboxylic acid with an aliphatic polyhydric alcohol compound or anamide of an unsaturated carboxylic acid with an aliphatic amine compoundis used.

Further, an addition reaction product of an ester or an amide of anunsaturated carboxylic acid having a hydroxyl group or a nucleophilicsubstituent such as an amino group or a mercapto group with anisocyanate or an epoxy, a dehydration condensation reaction product witha carboxylic acid, or the like can also be used. Further, an additionreaction product of an ester or an amide of an unsaturated carboxylicacid having an electrophilic substituent such as an isocyanate group oran epoxy group with an alcohol, an amine, or a thiol, further, asubstitution reaction product of an ester or an amide of an unsaturatedcarboxylic acid having a leaving substituent such as a halogen group ora tosyloxy group with an alcohol, an amine, or a thiol can also be used.

As a specific example of the radical polymerizable compound which is theester of an unsaturated carboxylic acid with an aliphatic polyhydricalcohol compound, for example, a (meth)acrylate ester is representative,and either a monofunctional (meth)acrylate or a polyfunctional(meth)acrylate can be used.

Specific examples of the monofunctional (meth) acrylate includetolyloxyethyl (meth) acrylate, phenyloxyethyl (meth) acrylate,cyclohexyl (meth) acrylate, ethyl (meth)acrylate, methyl (meth)acrylate,isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate,ethoxyethoxyethyl (meth) acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and 4-hydroxybutyl(meth) acrylate.

Specific examples of a difunctional (meth)acrylate include ethyleneglycol di(meth)acrylate, triethylene glycol di(meth)acrylate,1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate,propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate,hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate,tetraethylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate,dipentaerythritol di(meth)acrylate, and dipropylene glycoldi(meth)acrylate.

Specific examples of a trifunctional (meth) acrylate includetrimethylolpropane tri(meth)acrylate, trimethylolethane tri (meth)acrylate, alkylene oxide-modified tri(meth)acrylate oftrimethylolpropane, pentaerythritol tri(meth)acrylate, dipentaerythritoltri(meth)acrylate, trimethylolpropane tri((meth)acryloyloxypropyl)ether,isocyanuric acid alkylene oxide-modified tri(meth)acrylate, propionicacid dipentaerythritol tri(meth)acrylate, tri((meth)acryloyloxyethyl)isocyanurate, hydroxypivalaldehyde-modified dimethylolpropanetri(meth)acrylate, and sorbitol tri(meth)acrylate.

Specific examples of a tetrafunctional (meth)acrylate includepentaerythritol tetra(meth)acrylate, sorbitol tetra(meth)acrylate,ditrimethylolpropane tetra(meth)acrylate, propionic aciddipentaerythritol tetra(meth)acrylate, and ethoxylated pentaerythritoltetra(meth)acrylate.

Specific examples of a pentafunctional (meth)acrylate include sorbitolpenta(meth)acrylate and dipentaerythritol penta(meth)acrylate.

Specific examples of a hexafunctional (meth) acrylate includedipentaerythritol hexa (meth) acrylate, sorbitol hexa(meth)acrylate,alkylene oxide-modified hexa(meth)acrylate of phosphazene, andcaprolactone-modified dipentaerythritol hexa(meth)acrylate.

Examples of the polymerizable compound other than (meth)acrylatesinclude itaconate esters, crotonate esters, isocrotonate esters, andmaleate esters.

Examples of the itaconate esters include ethylene glycol diitaconate,propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanedioldiitaconate, tetramethylene glycol diitaconate, pentaerythritoldiitaconate, and sorbitol tetraitaconate.

Examples of the crotonate esters include ethylene glycol dicrotonate,tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, andsorbitol tetracrotonate.

Examples of the isocrotonate esters include ethylene glycoldiisocrotonate, pentaerythritol diisocrotonate, and sorbitoltetraisocrotonate.

Examples of the maleate esters include ethylene glycol dimaleate,triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitoltetramaleate.

Specific examples of a monomer of the amide of an unsaturated carboxylicacid with an aliphatic amine compound include methylenebis-acrylamide,methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide,1,6-hexamethylenebis-methacrylamide, diethylenetriamine trisacrylamide,xylylene bisacrylamide, xylylene bismethacrylamide, and (meth)acryloylmorpholine.

A urethane-based addition polymerizable compound which is produced by anaddition reaction between an isocyanate and a hydroxy group is alsopreferred.

In the invention, a cationic ring-opening polymerizable compound havingat least one cyclic ether group such as an epoxy group or an oxetanegroup in the molecule can be favorably used as a UV curable resin(polymerizable compound).

Examples of the cationic polymerizable compound include curablecompounds containing a ring-opening polymerizable group, and amongthese, heterocyclic group-containing curable compounds are morepreferred. Examples of such curable compounds include epoxy derivatives,oxetane derivatives, tetrahydrofuran derivatives, cyclic lactonederivatives, cyclic carbonate derivatives, cyclic imino ethers such asoxazoline derivatives, and vinyl ethers, and among these, epoxyderivatives, oxetane derivatives, and vinyl ethers are preferred.

Preferred examples of the epoxy derivatives include monofunctionalglycidyl ethers, polyfunctional glycidyl ethers, monofunctionalalicyclic epoxies, and polyfunctional alicyclic epoxies.

Specific examples of compounds of the glycidyl ethers include diglycidylethers, (for example, ethylene glycol diglycidyl ether, bisphenol Adiglycidyl ether, etc.), trifunctional or higher functional glycidylethers (for example, trimethylolethane triglycidyl ether,trimethylolpropane triglycidyl ether, glycerol triglycidyl ether,triglycidyl trishydroxyethyl isocyanurate, etc.), tetrafunctional orhigher functional glycidyl ethers (for example, sorbitol tetraglycidylether, pentaerythritol tetraglycidyl ether, polyglycidyl ethers ofcresol novolac resins, polyglycidyl ethers of phenolnovolac resins,etc.), alicyclic epoxies, polycyclohexyl epoxy methyl ethers of phenolnovolac resins, etc.), and oxetanes.

As the polymerizable compound, an alicyclic epoxy derivative can bepreferably used. An “alicyclic epoxy group” refers to a partialstructure in which a double bond of a cycloalkene ring of a cyclopentenegroup, a cyclohexene group, or the like is epoxidized with a suitableoxidizing agent such as hydrogen peroxide or a peroxy acid.

As the alicyclic epoxy compound, a polyfunctional alicyclic epoxycompound having two or more cyclohexene oxide groups or cyclopenteneoxide groups in one molecule is preferred. Specific examples of thealicyclic epoxy compound include 4-vinylcyclohexene dioxide,(3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexylcarboxylate,di(3,4-epoxycyclohexyl) adipate, di(3,4-epoxycyclohexylmethyl) adipate,bis(2,3-epoxycyclopentyl) ether, di(2,3-epoxy-6-methylcyclohexylmethyl)adipate, and dicyclopentadiene dioxide.

A normal glycidyl compound having an epoxy group but having no alicyclicstructure in the molecule can be used alone or can also be used incombination with the above-mentioned alicyclic epoxy compound.

Examples of such a normal glycidyl compound include a glycidyl ethercompound and a glycidyl ester compound, but it is preferred to use aglycidyl ether compound in combination.

Specific examples of the glycidyl ether compound include aromaticglycidyl ether compounds such as 1,3-bis(2,3-epoxypropyloxy)benzene, abisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenolnovolac type epoxy resin, a cresol novolac type epoxy resin, and atrisphenol methane type epoxy resin; and aliphatic glycidyl ethercompounds such as 1,4-butanediol glycidyl ether, glycerol triglycidylether, propylene glycol diglycidyl ether, and trimethylolpropanetritriglycidyl ether. Examples of the glycidyl ester include glycidylesters of linoleic acid dimers.

As the polymerizable compound, a compound having an oxetanyl group,which is a four-membered cyclic ether (hereinafter also simply referredto as “oxetane compound”), can be used. The oxetanyl group-containingcompound is a compound having one or more oxetanyl groups in onemolecule.

As the polymerization initiator, for example, azobisisobutyronitrile(AIBN), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide,2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, or the like can beused.

The composition according to the invention may be any as long as it hasfluidity when producing the shaped article, and may be, for example, acomposition which does not have fluidity (in the form of a solid) whenit is stored. Even in such a case, the composition can be generally madeto have sufficient fluidity by heating or the like when producing theshaped article.

The viscosity of the composition when producing the shaped article (forexample, in the case where the composition is ejected by an inkjetmethod, the viscosity when ejecting the composition) is preferably 2mPa·s or more and 30 mPa·s or less, more preferably 5 mPa·s or more and20 mPa·s or less.

According to this, the ejection stability of the composition by, forexample, an inkjet method can be made more excellent.

The “viscosity” as used herein refers to a value obtained by measurementusing an E-type viscometer (for example, VISCONIC ELD, manufactured byTokyo Keiki, Inc., or the like).

Incidentally, in the production of the shaped article, a plurality oftypes of compositions containing a cellulose derivative having a liquidcrystalline functional group and a liquid crystalline solvent having areactive functional group may be used.

For example, a composition as an ink (color ink) which contains acoloring agent and a composition as an ink (clear ink) which does notcontain a coloring agent may be used. According to this, for example, asthe composition to be applied to a region which has an effect on thecolor tone in appearance of the shaped article, the composition whichcontains a coloring agent is used, and as the composition to be appliedto a region which does not have an effect on the color tone inappearance of the shaped article, the composition which does not containa coloring agent can be used.

In addition, for example, a plurality of types of compositions whichcontain a coloring agent having a different composition may be used.According to this, by using these compositions in combination, anexpressible color reproduction range can be expanded.

In the case where a plurality of types of compositions (inks) are used,it is preferred to use at least a cyan ink, a magenta ink, and a yellowink. According to this, by using these compositions (inks) incombination, an expressible color reproduction range can be furtherexpanded.

Further, for example, by using a plurality of types of compositions(inks) having different types or contents of the cellulose derivativeand the liquid crystalline solvent, the properties such as rigidity andelasticity required for the respective regions of the shaped article canbe favorably adjusted.

Shaped Article

Next, the shaped article (three-dimensional shaped article) according tothe invention will be described.

The shaped article according to the invention is produced using thecomposition according to the invention as described above.

According to this, the shaped article which contains a cellulosicmaterial and has excellent strength and the like can be provided.

In particular, the shaped article according to the invention can befavorably produced using a production method described in detail later.

According to this, the shaped article which contains a cellulosicmaterial and has excellent strength and the like can be efficientlyproduced.

The shaped article according to the invention has such excellentcharacteristics, and therefore can be applied to various uses.

The use of the shaped article according to the invention is notparticularly limited, however, examples of the use include ornaments andexhibits such as dolls and figures; medical devices such as artificialdialyzers, implants, and stents; printing papers; optical members suchas lenses (including variable focus lenses), phase difference films, andpolarizing plates; gel materials such as culture scaffold materials tobe used for cultivation of various cells, various bacteria, etc.;vehicles such as bicycles; nursing care goods such as wheelchairs, andthe like, and constituent components thereof, and the like.

Among these, a stent is held in a state of being inserted into the bodyfor a long period of time, and is required to have excellent strength,durability, biocompatibility, and the like. However, according to theinvention, these requirements can be satisfied. Accordingly, when theinvention is applied to a stent, the effect of the invention can be moreremarkably exhibited. In particular, a stent to be applied to the bloodvessel is repeatedly subjected to a large pressure change over a longperiod of time, and also has a greater influence on life and health whena defect occurs among various types of stents, and therefore is requiredto have more excellent strength, durability, and safety. However,according to the invention, these requirements can be satisfied.

Further, the shaped article according to the invention may be applied toany of prototypes, mass-produced products, and custom-made products.

Shaped Article Production Method

Next, a shaped article production method according to the invention willbe described.

The shaped article according to the invention may be any as long as itis produced using the composition according to the invention asdescribed above, and the production method for the shaped article is notparticularly limited.

Examples of the shaped article production method according to theinvention include a method including supplying the composition accordingto the invention to a given region, and allowing a chemical reactioninvolving the reactive functional group of the liquid crystallinesolvent constituting the composition to proceed.

According to this, a shaped article production method capable ofefficiently producing a shaped article which contains a cellulosicmaterial and has excellent strength and the like can be provided.

More specific examples of the shaped article production method accordingto the invention include various molding methods such as compressionmolding, extrusion molding, and injection molding. Further, a method forsubjecting a bulk material produced through steps as described above toa machining process such as cutting, grinding, or polishing may beadopted.

In particular, as the shaped article production method according to theinvention, a three-dimensional shaping method (a method for producing athree-dimensional shaped article by performing a layer forming step offorming a layer using the composition a plurality of times and stackingthe layers on one another) as described below can be used.

According to this, even a shaped article required to have highdimensional accuracy or a shaped article having a complicated shape canbe efficiently produced with sufficient dimensional accuracy. Further,the production method can be favorably applied also to the production ofa plurality of types of shaped articles having different shapes andsizes.

Hereinafter, a case where a three-dimensional shaping method is appliedwill be described as a specific example of the shaped article productionmethod.

First Embodiment

FIGS. 1A 1H are cross-sectional views schematically showing respectivesteps in a first embodiment of the shaped article production methodaccording to the invention.

As shown in FIGS. 1A to 1H, the production method of this embodiment isconfigured as follows. The method includes a layer forming step (FIGS.1A and 1D) in which a layer P1 having a given thickness is formed in aregion surrounded by a side surface support part (frame body) 45 using alayer forming composition containing particles (particle-containingcomposition) P1′, a composition application step (FIGS. 1B and 1E) inwhich a composition (ink) P12 which is in the form of a liquid andcontains a cellulose derivative having a liquid crystalline functionalgroup and a liquid crystalline solvent having a reactive functionalgroup as described above is applied to the layer P1 by an inkjet method,and a solidification step (FIGS. 1C and 1F) in which the composition P12applied to the layer P1 is solidified (cured) by a chemical reactioninvolving the liquid crystalline solvent. These steps are sequentiallyand repeatedly performed (FIG. 1G), and thereafter, the method furtherincludes an unbound particle removal step (FIG. 1H) in which among theparticles constituting the respective layers P1, the particles which arenot bound to one another (unnecessary part) by the solidified material(cured material) of the composition P12 are removed.

Hereinafter, the respective steps will be described.

Layer Forming Step

In the layer forming step, a layer P1 having a given thickness is formedusing a layer forming composition containing particles(particle-containing composition) P1′ (FIGS. 1A and 1D).

In this manner, by using the layer forming composition containingparticles P1′, the dimensional accuracy of a shaped article(three-dimensional shaped article) P10 to be obtained finally can bemade excellent. Further, the heat resistance, mechanical strength, andthe like of the shaped article P10 can be made more excellent.

The layer forming composition P1′ will be described in detail later.

In this step, by using a flattening unit, the layer P1 is formed suchthat the surface is flattened.

In the first layer forming step, the layer P1 is formed to a giventhickness on the surface of a stage 41 (FIG. 1A). At this time, the sidesurface of the stage 41 and the side surface support part 45 are in aclose contact (abutment) state, so that the layer forming compositionP1′ is prevented from falling between the stage 41 and the side surfacesupport part 45.

In each layer forming step after the first layer forming step, a newlayer P1 (second layer) is formed on the surface of the layer P1 (firstlayer) formed in the previous step (FIG. 1D). At this time, the sidesurface of the layer P1 on the stage 41 (in the case where a pluralityof layers P1 are present on the stage 41, at least the layer P1 providedon the uppermost side) and the side surface support part 45 are in aclose contact (abutment) state, so that the layer forming compositionP1′ is prevented from falling between the stage 41 and the layer P1 onthe stage 41.

In this step, the layer forming composition P1′ may be heated. By doingthis, for example, in the case where the layer forming composition P1′contains a molten component, the layer forming composition P1′ can bemore favorably formed into a paste.

The viscosity of the layer forming composition P1′ in this step ispreferably 500 mPa·s or more and 1,000,000 mPa·s or less. According tothis, the occurrence of an undesirable variation in the film thicknessof the layer P1 to be formed can be more effectively prevented.

The thickness of the layer P1 to be formed in this step is notparticularly limited, but is, for example, preferably 20 μm or more and500 μm or less, more preferably 30 μm or more and 150 μm or less.According to this, while making the productivity of the shaped articleP10 sufficiently excellent, the occurrence of undesirable irregularitiesor the like in the shaped article P10 to be produced is more effectivelyprevented, and the dimensional accuracy of the shaped article P10 can bemade more excellent.

Composition Application Step (Ink Application Step)

After the layer P1 is formed in the layer forming step, a composition(ink) P12 which is in the form of a liquid and contains a cellulosederivative having a liquid crystalline functional group and a liquidcrystalline solvent having a reactive functional group is applied to thelayer P1 by an inkjet method (FIGS. 1B and 1E).

In this embodiment, the composition P12 functions as a bonding solution(binding solution) for binding the particles constituting the layer P1.

The composition P12 contains a cellulose derivative having a liquidcrystalline functional group and also a liquid crystalline solventhaving a reactive functional group, and the affinity between thecellulose derivative and the liquid crystalline solvent is excellent.Due to this, an undesirable variation in the formulation in thecomposition P12 is prevented. As a result, an undesirable variation inthe formulation of the composition P12 at the respective regions towhich the composition P12 is applied can be prevented.

In this step, the composition P12 is selectively applied only to aregion corresponding to a tangible part (a region where a tangible bodyis present) of the shaped article P10 to be produced in the layer P1.

By doing this, the particles constituting the layer P1 are bound to oneanother, whereby a bound part (tangible part) P13 having a desired shapecan be formed in the end.

This step may be performed while heating the composition P12.

According to this, the fluidity of the composition P12 can be made morefavorable, so that the application pattern, the application amount, andthe like of the composition P12 can be more favorably adjusted, andthus, the dimensional accuracy and the like of the shaped article P10 tobe obtained finally can be made more excellent. Further, the liquidcrystalline solvent and the cellulose derivative contained in thecomposition P12 can be more favorably aligned, and thus, the mechanicalstrength of the shaped article P10 to be obtained finally can be mademore excellent.

The temperature of the composition P12 in this step is preferably 10° C.or higher and 100° C. or lower, more preferably 30° C. or higher and 95°C. or lower, further more preferably 35° C. or higher and 90° C. orlower.

According to this, the effect as described above can be more remarkablyexhibited while sufficiently preventing undesirable denaturation,deterioration, or the like of the materials.

Further, in this step, a region to which the composition P12 is to beapplied (in this embodiment, the layer P1 to which the composition P12is applied, and in the below-mentioned second embodiment, in the casewhere a tangible part P16 in the first layer is formed, a stage 41, inthe case where a tangible part P16 in the second or subsequent layer isformed, the layer P1 to which a tangible part forming ink P16′ to beused for forming the tangible part P16 is applied) may be heated.

According to this, the application pattern, the application amount, andthe like of the composition P12 can be more favorably adjusted, andthus, the dimensional accuracy and the like of the shaped article P10 tobe obtained finally can be made more excellent. Further, thepermeability of the composition P12 into the layer P1 can be madeexcellent, and also the liquid crystalline solvent and the cellulosederivative contained in the composition P12 can be more favorablyaligned, and thus, the mechanical strength of the shaped article P10 tobe obtained finally can be made more excellent.

The temperature of the region to which the composition P12 is to beapplied in this step is preferably 10° C. or higher and 100° C. orlower, more preferably 30° C. or higher and 95° C. or lower, furthermore preferably 35° C. or higher and 90° C. or lower.

According to this, the effect as described above is more remarkablyexhibited while sufficiently preventing undesirable denaturation,deterioration, or the like of the materials.

Further, in this step, when the composition P12 is applied in this step,the cellulose derivative contained in the composition P12 is preferablyin a dissolved state in the liquid crystalline solvent in thecomposition P12.

According to this, the liquid crystalline solvent and the cellulosederivative contained in the composition P12 can be more favorablyaligned, and thus, the mechanical strength of the shaped article P10 tobe obtained finally can be made more excellent.

In this embodiment, the composition P12 is applied by an inkjet method,and therefore, even if the application pattern of the composition P12has a finer shape, the composition P12 can be applied with higherreproducibility. As a result, the dimensional accuracy of the shapedarticle P10 to be obtained finally can be further increased. Further, inthe related art, in the case where a shaped article constituted by amaterial containing a cellulosic material is tried to be produced usingan inkjet method, a problem that the dimensional accuracy or the like ofthe shaped article is low occurred more remarkably. However, accordingto the invention, even in the case where an inkjet method is used, theoccurrence of such a problem can be reliably prevented.

The composition P12 may be applied onto a member having been subjectedto an alignment treatment. That is, the stage 41 may have a surfacehaving been subjected to an alignment treatment.

According to this, the liquid crystalline functional group of thecellulose derivative and the liquid crystalline functional group of theliquid crystalline solvent contained in the composition P12 can be morefavorably aligned, and thus, the mechanical strength, durability,reliability, and the like of the shaped article P10 to be obtainedfinally can be made more excellent.

In the case where the surface of the stage 41 has been subjected to analignment treatment, also in each layer P1 formed after forming thefirst layer P1, in a region to which the composition P12 is applied, theliquid crystalline functional group of the cellulose derivative and theliquid crystalline functional group of the liquid crystalline solventare affected by the layer P1 (the layer P1 in which the liquidcrystalline functional group is aligned) on the lower side thereof, andtherefore, even if the layer is not in direct contact with the stage,the liquid crystalline functional group of the cellulose derivative andthe liquid crystalline functional group of the liquid crystallinesolvent are favorably aligned. That is, for each layer P1 formed afterforming the first layer P1, the layer P1 on the lower side thereoffunctions as a member having been subjected to an alignment treatment.

As the alignment treatment, a method such as a rubbing treatment isfavorably used.

Further, as a material of the surface of the stage 41, for example, amaterial such as polyimide for which an alignment treatment is favorablyperformed can be used.

Solidification Step (Curing Step)

After the composition P12 is applied to the layer P1 in the compositionapplication step (ink application step), the composition P12 in the formof a liquid is solidified (cured), whereby a bound part (tangible part)P13 is formed (FIGS. 1C and 1F).

In this step, at least a chemical reaction (a chemical reaction to forma covalent bond) involving the reactive functional group of the liquidcrystalline solvent is performed. According to this, the hardness of thebound part (tangible part) P13 to be formed can be increased, and thus,the mechanical strength, durability, and reliability of the shapedarticle P10 to be obtained finally can be made excellent.

Further, in the case where the composition P12 contains a cellulosederivative having a reactive functional group, a chemical reaction (achemical reaction to form a covalent bond) involving the cellulosederivative may be performed. According to this, the hardness of thebound part (tangible part) P13 to be formed can be further increased,and thus, the mechanical strength, durability, and reliability of theshaped article P10 to be obtained finally can be made more excellent.

In this step, in the case where a chemical reaction (curing reaction) toform a covalent bond is performed, the chemical reaction can beperformed by, for example, heating, irradiation with an energy ray (forexample, a light such as a UV light, an electron beam, a positron beam,a neutron beam, an a beam, an ion beam, etc.), or the like.

In particular, in the case where the chemical reaction is allowed toproceed by heating, the structure of the production apparatus for theshaped article P10 can be simplified. Further, even if the raw materialof the shaped article P10 is a material having a low lighttransmittance, a desired reaction can be allowed to favorably proceed.

In the case where the chemical reaction is allowed to proceed byheating, the heating temperature is preferably 85° C. or higher and 180°C. or lower, more preferably 90° C. or higher and 150° C. or lower.

Further, in the case where the chemical reaction is allowed to proceedby light irradiation, the productivity of the shaped article P10 can bemade more excellent while more effectively preventing undesirabledenaturation, deterioration, or the like of the materials.

In the case where the chemical reaction is allowed to proceed by lightirradiation, as the light, for example, a UV light, an IR light, avisible light, an X-ray, a microwave, a radio wave, or the like can beused, however, it is preferred to use a UV light.

According to this, the productivity of the shaped article P10 can bemade more excellent, and also the structure of the production apparatusfor the shaped article P10 can be prevented from being complicated, andthus, the production cost of the shaped article P10 can be kept low.

Further, in the case where the chemical reaction is allowed to proceedby UV irradiation, the peak wavelength of the UV light is preferably 250nm or more and 400 nm or less. Further, the UV irradiation time for eachregion to be cured is preferably 30 seconds or more and 60 seconds orless.

The composition application step (ink application step) and thesolidification step may be performed concurrently. That is, beforeforming the entire pattern of the entire one layer P1, the reaction maybe allowed to proceed sequentially from a region to which thecomposition P12 is applied.

Unbound Particle Removal Step

After the steps as described above are performed repeatedly, as apost-treatment step, an unbound particle removal step (FIG. 1H) in whichamong the particles constituting the respective layers P1, the particleswhich are not bound to one another (unbound particles) by the solidifiedmaterial (cured material) of the composition P12 are removed isperformed. By doing this, the shaped article P10 is taken out.

Examples of a specific method of this step include a method in which theunbound particles (unnecessary part) are removed by brushing with abrush or the like, a method in which the unbound particles (unnecessarypart) are removed by suction, a method in which a gas such as air isblown, a method in which a liquid such as water is applied (for example,a method in which a stacked body obtained as described above is soakedin a liquid, a method in which a liquid is blown, etc.), and a method inwhich vibration such as ultrasonic vibration is applied. Further, two ormore methods selected from these methods can be performed incombination. More specifically, a method in which a gas such as air isblown to the stacked body, and thereafter, the stacked body is soaked ina liquid such as water, a method in which ultrasonic vibration isapplied to the stacked body while soaking the stacked body in a liquidsuch as water, and the like can be exemplified. Above all, it ispreferred to adopt a method in which a liquid containing water isapplied to the stacked body obtained as described above (particularly, amethod in which the stacked body is soaked in a liquid containingwater).

Second Embodiment

Next, a second embodiment of the shaped article production method willbe described.

FIGS. 2A to 2F are cross-sectional views schematically showingrespective steps in a second embodiment of the shaped article productionmethod according to the invention. In the following description,different points from the above-mentioned embodiment will be mainlydescribed, and the description of the same matter will be omitted.

As shown in FIG. 2A to 2F, the production method of this embodiment isconfigured as follows. The method includes an ink application step (2 aand 2 c) in which a tangible part forming ink P16′ as the compositionwhich is in the form of a liquid and contains a cellulose derivativehaving a liquid crystalline functional group and a liquid crystallinesolvent having a reactive functional group and is used for forming atangible part P16 and a support part forming ink P17′ which is used forforming a support part P17 for supporting the tangible part P16 areejected in a given pattern by an inkjet method, and a solidificationstep (2 b and 2 d) in which the ejected tangible part forming ink P16′and support part forming ink P17′ are solidified (cured), therebyforming the tangible part P16 and the support part P17. These steps aresequentially and repeatedly performed, thereby obtaining a preform bodyP10′ (2 e), and thereafter, the method further includes a support partremoval step (2 f) in which the support part P17 is removed.

In this manner, in this embodiment, by the ink application step and thesolidification step (curing step), the layer P1 is formed. That is, inthis embodiment, the layer forming step includes the ink applicationstep and the solidification step.

In this manner, in this embodiment, the layer is formed using the ink tobe ejected by an inkjet method as the composition for forming the layerwithout forming a layer while flattening the composition containingparticles by a flattening unit.

According to this, the composition can be selectively applied to anecessary place in a shaping region (a region on a stage 41), andtherefore, the wasting of the material in the production of the shapedarticle P10 can be prevented and suppressed. Due to this, this isadvantageous from the viewpoint of reduction in the production cost ofthe shaped article P10 and resource saving. Further, the number of stepscan be reduced as a whole, and also a treatment such as recovery of thematerial or the like can be omitted or simplified, and thus, theproductivity of the shaped article P10 can be made more excellent.

Hereinafter, the respective steps will be described.

Ink Application Step (Ink Ejection Step)

In the ink application step, a tangible part forming ink P16′ as thecomposition which is in the form of a liquid and contains a cellulosederivative having a liquid crystalline functional group and a liquidcrystalline solvent having a reactive functional group and a supportpart forming ink P17′ which contains a curable resin (curable component)are ejected in a given pattern by an inkjet method (2 a and 2 c).

More specifically, the tangible part forming ink P16′ is applied to aregion which is to become the tangible part P16 of the shaped article(three-dimensional shaped article) P10, and the support part forming inkP17′ is applied to a region which is adjacent to a region to become theoutermost layer of the tangible part P16 of the shaped article P10 andon the surface side of the outermost layer.

In the first ink application step, on the stage 41, the inks (thetangible part forming ink P16′ and the support part forming ink P17′)are ejected (2 a), and in each ink application step after the first inkapplication step, on the layer P1, the inks (the tangible part formingink P16′ and the support part forming ink P17′) are ejected (2 c).

In this manner, in this embodiment, not only the tangible part formingink P16′ (the ink corresponding to the composition P12 in the firstembodiment described above) is applied to the region which is to becomethe tangible part P16 of the shaped article P10, but also the ink (thesupport part forming ink P17′) is applied to the surface side thereof.

According to this, by forming the support part P17 by applying thesupport part forming ink P17′, even if a layer constituting the shapedarticle P10 (second layer) has a portion protruding from the outerperipheral portion of the layer (first layer) lower than this layer (forexample, in the drawing, a relationship between the first layer and thesecond layer from the bottom, a relationship between the second layerand the third layer from the bottom, a relationship between the fifthlayer and the sixth layer from the bottom, and a relationship betweenthe sixth layer and the seventh layer from the bottom), the support partP17 in the lower layer (first layer) can favorably support the tangiblepart forming ink P16′ for forming the upper layer (second layer). Due tothis, undesirable deformation (particularly, sagging or the like) of thetangible part P16 can be favorably prevented, and thus, the dimensionalaccuracy of the shaped article P10 to be obtained finally can be mademore excellent.

Further, in this step, the inks (the tangible part forming ink P16′ andthe support part forming ink P17′) are applied by an inkjet method, andtherefore, even if the application pattern of the inks (the tangiblepart forming ink P16′ and the support part forming ink P17′) has a fineshape, the inks can be applied with high reproducibility. As a result,the dimensional accuracy of the shaped article P10 to be obtainedfinally can be further increased, and also the control of the surfaceshape and appearance of the shaped article P10 can be more favorablyperformed.

The support part forming ink P17′ will be described in detail later.

The amount of the ink to be applied in this step is not particularlylimited, but is preferably such that the thickness of the layer P1 to beformed in the subsequent solidification step becomes 20 μm or more and500 μm or less, more preferably 30 μm or more and 150 μm or less.

According to this, while making the productivity of the shaped articleP10 sufficiently excellent, the occurrence of undesirable irregularitiesor the like in the shaped article P10 to be produced is more effectivelyprevented, and the dimensional accuracy of the shaped article P10 can bemade more excellent. In addition, the surface state and appearance ofthe shaped article P10 to be obtained finally can be more favorablycontrolled.

Solidification Step (Layer Forming Step)

After the inks (the tangible part forming ink P16′ and the support partforming ink P17′) are applied (ejected) in the ink application step, thetangible part forming ink P16′ is solidified (cured) and also thecurable component (curable resin) contained in the support part formingink P17′ is cured (2 b and 2 d). By doing this, the layer P1 having thetangible part P16 and the support part P17 is obtained. That is, theregion to which the tangible part forming ink P16′ is applied becomesthe tangible part P16, and the region to which the support part formingink P17′ is applied becomes the support part P17.

This step can be performed by, for example, heating, irradiation with anenergy ray (for example, a light such as a UV light, an electron beam, apositron beam, a neutron beam, an a beam, an ion beam, etc.), or thelike, although the method varies depending on the constituent materialof the tangible part forming ink P16′ and the type of the curablecomponent (curable resin) contained in the support part forming ink P17′.

In particular, in the case where the tangible part P16 and the supportpart P17 are formed by heating, the structure of the productionapparatus for the shaped article P10 can be simplified. Further, even ifthe raw material of the shaped article P10 is a material having a lowlight transmittance, a desired reaction can be allowed to favorablyproceed.

In the case where the tangible part P16 and the support part P17 areformed by heating, the heating temperature is preferably 50° C. orhigher and 180° C. or lower, more preferably 60° C. or higher and 150°C. or lower.

Further, in the case where the tangible part P16 and the support partP17 are formed by light irradiation, the productivity of the shapedarticle P10 can be made more excellent while more effectively preventingundesirable denaturation, deterioration, or the like of the materials.

In the case where the tangible part P16 and the support part P17 areformed by light irradiation, as the light, for example, a UV light, anIR light, a visible light, an X-ray, a microwave, a radio wave, or thelike can be used, however, it is preferred to use a UV light.

According to this, the productivity of the shaped article P10 can bemade more excellent, and also the structure of the production apparatusfor the shaped article P10 can be prevented from being complicated, andthus, the production cost of the shaped article P10 can be kept low.

In the above explanation, it is described that the inks are applied in ashape and a pattern corresponding to the layer P1 and thereafter theentire layer (the layer corresponding to the layer P1) constituted bythe inks is cured, however, in the invention, in at least a portion ofthe region, the ejection of the ink and the curing of the ink may beperformed concurrently. That is, before forming the entire pattern ofthe entire one layer P1, a curing reaction may be allowed to proceedsequentially from a region to which the ink is applied in at least aportion of the region corresponding to the layer P1. However, for atleast a contact portion between the tangible part forming ink P16′ andthe support part forming ink P17′ (a portion where the tangible part P16and the support part P17 should be in contact with each other), it ispreferred that the curing treatment is performed simultaneously, and thecuring treatment for the tangible part forming ink P16′ and the curingtreatment for the support part forming ink P17′ are not performedseparately.

In this step, it is not necessary to completely cure the curablecomponent contained in the ink. For example, at the end of this step,the support part forming ink P17′ may be in an incompletely cured stateand the tangible part forming ink P16′ may be cured to a higher curingdegree than the support part forming ink P17′.

According to this, the support part removal step, which will bedescribed in detail later, can be easily performed, and the productivityof the shaped article P10 can be further improved.

Further, at the end of this step, the tangible part forming ink P16′ maybe brought to a state where the tangible part forming ink P16′ is curedin an incomplete state. Even in such a case, for example, afterperforming a subsequent step (for example, the “ink application step” orthe like after forming the layer P1 on the lower side in thesolidification step (curing step)), by performing a main curingtreatment for increasing the curing degree of the tangible part formingink P16′ (tangible part P16) in an incompletely cured state, themechanical strength and the like of the shaped article P10 to beobtained finally can be made excellent. Further, by applying the ink forforming the upper layer in a state where the tangible part forming inkP16′ (lower layer) is cured in an incomplete state, the adhesivenessbetween the layers can be made more excellent.

Support Part Removal Step

After a series of steps as described above are performed repeatedly, thesupport part P17 is removed (2 f). By doing this, the shaped article P10is obtained.

Examples of a method for removing the support part P17 include a methodin which the support part P17 is selectively dissolved and removed usinga liquid which selectively dissolves the support part P17, and a methodin which a liquid for which the support part P17 has higherabsorbability than the tangible part P16 is used and the support partP17 is made to selectively absorb the liquid to swell the support partP17, or to decrease the mechanical strength of the support part P17, andthen, the support part P17 is exfoliated or disrupted.

The liquid to be used in this step varies depending on the constituentmaterials or the like of the tangible part P16 and the support part P17,however, examples thereof include water, alcohols such as methanol,ethanol, isopropyl alcohol, n-propyl alcohol, butanol, and isobutanol,glycerin, and glycols such as ethylene glycol, diethylene glycol,triethylene glycol, propylene glycol, and dipropylene glycol, and oneliquid or a combination of two or more liquids selected from these canbe used. Further, the liquid may be a liquid mixed with a water-solublesubstance which generates a hydroxide ion such as sodium hydroxide,potassium hydroxide, sodium hydrogen carbonate, or an organic amine forincreasing the solubility of the support part, a surfactant whichfacilitates the separation of the exfoliated support part, or the like.

A method for applying the liquid to the preform body P10′ is notparticularly limited, and for example, a soaking method, a sprayingmethod, a coating method, a variety of printing methods, and the likecan be adopted.

In the above explanation, it is described that the liquid is used in thestep, however, a substance having the same function (for example, asolid, a gas, a supercritical fluid, or the like) may be used.

Further, when or after the liquid is applied, ultrasonic vibration maybe applied.

By doing this, the removal of the support part P17 can be accelerated,and thus, the productivity of the shaped article P10 can be made moreexcellent.

In the above explanation, it is described that the support part formingink P17′ is applied so as to come in contact with the tangible partforming ink P16′ in the entire region which is to become the outermostlayer of the shaped article P10, however, the support part forming inkP17′ maybe applied so as to come in contact with the tangible partforming ink P16′ only in a portion of the region which is to become theoutermost layer of the shaped article P10. Further, in the case wherethe shaped article P10 to be produced has a shape which can be producedwithout forming the support part P17, the support part forming ink P17′may not be used.

In the case where the formation of the support part is not needed due tothe shape or the like of the shaped article P10 to be produced, thelayer P1 may be formed using only the tangible part forming ink.

Shaped Article Production Apparatus

Next, a production apparatus (shaped article production apparatus) whichcan be used for producing the shaped article (three-dimensional shapedarticle) according to the invention will be described.

First Embodiment

FIG. 3 is a cross-sectional view schematically showing a firstembodiment of the production apparatus to be used for producing theshaped article according to the invention.

A shaped article production apparatus 100 shown in FIG. 3 produces ashaped article P10 by repeatedly forming a layer P1 using a layerforming composition containing particles (particle-containingcomposition) P1′, and stacking the formed layers P1.

As shown in FIG. 3, the shaped article production apparatus 100 includesa control section 2, a layer forming composition supply section(particle-containing composition supply section) 3 which supplies thelayer forming composition containing particles P1′, a layer formingsection 4 which forms the layer P1 using the layer forming compositionP1′ supplied from the layer forming composition supply section 3, aliquid composition ejection section (liquid composition applicationunit) 5 which ejects a composition (ink) P12 in the form of a liquid tothe layer P1, and an energy ray irradiation unit (solidification unit orbond forming unit) 6 which irradiates an energy ray for solidifying(curing) the composition P12 in the form of a liquid.

The control section 2 includes a computer 21 and a drive control section22.

The computer 21 is a common desk top computer or the like configured toinclude a CPU, a memory, etc. therein. The computer 21 digitizes theshape of the shaped article (three-dimensional shaped article) P10 asmodel data, and outputs cross-sectional data (slice data) obtained byslicing the shaped article P10 into a plurality of parallel layers ofthin cross sections to the drive control section 22.

The drive control section 22 functions as a control unit forindividually driving the layer forming section 4, the liquid compositionejection section 5, and the energy ray irradiation unit 6. Specifically,for example, the drive control section 22 controls the ejection patternand the ejection amount of the composition P12 in the form of a liquidby the liquid composition ejection section 5, the supply amount of thelayer forming composition P1′ from the layer forming composition supplysection 3, the descent amount of a stage 41, and the like.

The layer forming composition supply section 3 is configured to moveunder the command of the drive control section 22 and supply the layerforming composition P1′ held therein to a layer forming compositiontemporary placing section 44.

The layer forming section 4 includes the layer forming compositiontemporary placing section 44 which temporarily holds the layer formingcomposition P1′ supplied from the layer forming composition supplysection 3, a squeegee (flattening unit) 42 which forms the layer P1while flattening the layer forming composition P1′ held by the layerforming composition temporary placing section 44, a guide rail 43 whichregulates the movement of the squeegee 42, the stage 41 which supportsthe formed layer P1, and a side surface support section (frame body) 45which surrounds the stage 41.

When a new layer P1 is formed on a previously formed layer P1, thepreviously formed layer P1 is moved relatively downward with respect tothe side surface support section 45. By doing this, the thickness of thelayer P1 to be newly formed is defined.

In particular, in this embodiment, when a new layer P1 is formed on apreviously formed layer P1, the stage 41 sequentially descends by agiven amount under the command of the drive control section 22. In thismanner, since the stage 41 is configured to be able to move in theZ-axis direction (vertical direction), the number of members to be movedfor adjusting the thickness of the layer P1 when the new layer P1 isformed can be decreased, and therefore, the structure of the shapedarticle production apparatus 100 can be further simplified.

The stage 41 has a flat surface (a region to which the layer formingcomposition P1′ is applied).

According to this, the layer P1 having a highly uniform thickness can beeasily and reliably formed. Further, in the shaped article P10 to beproduced, the occurrence of undesirable deformation or the like can beeffectively prevented.

The stage 41 is preferably constituted by a material with a highstrength. Examples of the constituent material of the stage 41 includevarious metal materials such as stainless steel.

Further, the surface (the region to which the layer forming compositionP1′ is applied) of the stage 41 may be subjected to a surface treatment.By doing this, for example, the adhesion of the constituent material ofthe layer forming composition P1′ or the constituent material of thecomposition P12 to the stage 41 is more effectively prevented, or thedurability of the stage 41 is made more excellent, and thus, the stableproduction of the shaped article P10 can be achieved for a longer periodof time. Examples of a material to be used for the surface treatment ofthe surface of the stage 41 include fluororesins such aspolytetrafluoroethylene. Further, for the stage 41, for example, amaterial such as polyimide subjected to an alignment treatment can beused. According to this, the effect as described above is obtained.

The squeegee 42 has an elongated shape extending in the Y-axis directionand includes a blade having a sharp edge shape at a lower tip end.

The length of the blade in the Y-axis direction is equal to or longerthan the width (the length in the Y-axis direction) of the stage 41(shaping region).

The shaped article production apparatus 100 may include a vibrationmechanism (not shown) for giving small vibration to the blade so as tosmoothly diffuse the layer forming composition P1′ with the squeegee 42.

The side surface support section 45 has a function to support the sidesurface of the layer P1 formed on the stage 41. The side surface supportsection 45 also has a function to define the area of the layer P1 whenforming the layer P1.

Further, a surface (a region which can come in contact with the layerforming composition P1′) of the side surface support section 45 may besubjected to a surface treatment. By doing this, for example, theadhesion of the constituent material of the layer forming compositionP1′ or the constituent material of the composition P12 to the sidesurface support section 45 is more effectively prevented, or thedurability of the side surface support section 45 is made moreexcellent, and thus, the stable production of the shaped article P10 canbe achieved for a longer period of time. Further, when the previouslyformed layer P1 is moved relatively downward with respect to the sidesurface support section 45, the occurrence of an undesirable disturbanceof the layer P1 can be effectively prevented. As a result, thedimensional accuracy and reliability of the shaped article P10 to beobtained finally can be made more excellent. Examples of a material tobe used for the surface treatment of the surface of the side surfacesupport section 45 include fluororesins such as polytetrafluoroethylene.

The liquid composition application unit (liquid composition ejectionsection) 5 applies the composition P12 in the form of a liquid to thelayer P1.

By including such a liquid composition application unit 5, themechanical strength of the shaped article P10 can be easily and reliablymade excellent.

In particular, in this embodiment, the liquid composition applicationunit 5 is a liquid composition ejection section which ejects thecomposition P12 in the form of a liquid by an inkjet method.

According to this, the composition P12 in the form of a liquid can beapplied in a fine pattern, and even if the shaped article P10 has a finestructure, the shaped article P10 can be produced with higherproductivity.

As a liquid droplet ejection system (a system of the inkjet method), apiezo system, a system for ejecting the composition P12 in the form of aliquid by a bubble generated by heating the composition P12 in the formof a liquid, or the like can be used, however, from the viewpoint thatthe constituent components of the composition P12 are hardly denatured,and the like, a piezo system is preferred.

In the liquid composition ejection section (liquid compositionapplication unit) 5, the pattern to be formed for each layer P1 and theamount of the composition P12 to be applied to each part of the layer P1are controlled by the command of the drive control section 22. Theejection pattern, the ejection amount, and the like of the compositionP12 using the liquid composition ejection section (liquid compositionapplication unit) 5 are determined based on the slice data.

The energy ray irradiation unit (solidification unit or bond formingunit) 6 irradiates an energy ray for solidifying (curing) thecomposition P12 in the form of a liquid applied to the layer P1.

In particular, in the configuration shown in the drawing, the energy rayirradiation unit (solidification unit or bond forming unit) 6 isprovided on the upstream and downstream of the liquid compositionejection section (liquid composition application unit) 5 in a scanningdirection.

According to this, the bond formation can be performed by the energy rayirradiation unit (solidification unit or bond forming unit) 6 on bothforward and backward paths, and therefore, the productivity of theshaped article P10 can be made more excellent.

Second Embodiment

Next, a second embodiment of the production apparatus (shaped articleproduction apparatus) to be used for producing the shaped articleaccording to the invention will be described.

FIG. 4 is a cross-sectional view schematically showing a secondembodiment of the production apparatus to be used for producing theshaped article according to the invention. In the following description,different points from the above-mentioned embodiment will be mainlydescribed, and the description of the same matter will be omitted.

A shaped article production apparatus 100 produces a shaped article(three-dimensional shaped article) P10 by repeatedly forming a layer P1using a tangible part forming ink P16′ and a support part forming inkP17′, and stacking the formed layers P1.

As shown in FIG. 4, the shaped article production apparatus 100 includesa control section 2, a stage 41, a tangible part forming ink applicationunit 8 which ejects the tangible part forming ink P16′ as thecomposition in the form of a liquid, a support part forming inkapplication unit 9 which ejects the support part forming ink P17′, andan energy ray irradiation unit (solidification unit or bond formingunit) 6 which irradiates an energy ray for curing the tangible partforming ink P16′ and the support part forming ink P17′.

The tangible part forming ink application unit 8 ejects the tangiblepart forming ink P16′ by an inkjet method.

By including such a tangible part forming ink application unit 8, only adesired amount of the tangible part forming ink P16′ can be applied to adesired region in a fine pattern, and thus, even if the shaped articleP10 has a fine structure, the shaped article P10 can be produced withhigher productivity.

As a liquid droplet ejection system (a system of the inkjet method), apiezo system, a system for ejecting the ink by a bubble generated byheating the ink, or the like can be used, however, from the viewpointthat the constituent components of the ink are hardly denatured, and thelike, a piezo system is preferred.

In the tangible part forming ink application unit 8, the pattern to beformed, the amount of the tangible part forming ink P16′ to be applied,and the like are controlled by the command of the drive control section22. The ejection pattern, the ejection amount, and the like of thetangible part forming ink P16′ using the tangible part forming inkapplication unit 8 are determined based on the slice data.

According to this, a necessary and sufficient amount of the tangiblepart forming ink P16′ can be applied to a target region, and thus, thetangible part P16 in a desired pattern can be reliably formed, and thedimensional accuracy and the mechanical strength of the shaped articleP10 can be more reliably made excellent. Further, in the case where thetangible part forming ink P16′ contains a coloring agent, a desiredcolor tone, design, and the like can be reliably obtained.

The tangible part forming ink application unit 8 is configured to beable to relatively move in the X-axis and Y-axis directions with respectto the stage, and also to be able to move in the Z-axis direction.

According to this, even when the layers P1 are stacked, a distancebetween a nozzle surface (a tip end of an ejection section) of thetangible part forming ink application unit 8 and a place where thetangible part forming ink P16′ lands can be kept at a predeterminedvalue.

The support part forming ink application unit 9 ejects the support partforming ink P17′ by an inkjet method.

By including such a support part forming ink application unit 9, only adesired amount of the support part forming ink P17′ can be applied to adesired region in a fine pattern, and thus, even if the shaped articleP10 to be produced has a fine structure, the support part P17 having adesired size and a desired shape can be formed in a desired region, andthe surface shape and appearance of the shaped article P10 can be morereliably controlled. Further, the productivity of the shaped article P10can be made more excellent.

A liquid droplet ejection system (a system of the inkjet method),controlling, driving, etc. for the support part forming ink applicationunit 9 are the same as those for the tangible part forming inkapplication unit 8 described above.

Although not shown in the drawing, the shaped article productionapparatus 100 may include a support part removal unit for removing thesupport part P17 and a drying unit for drying the shaped article P10after removing the support part P17.

Examples of the support part removal unit include a unit whichmechanically disrupts and removes the support part P17, a tank in whicha liquid as described above is held and the preform. body P10′ issoaked, a liquid spraying unit which sprays a liquid as described aboveonto the preform body P10′, and a liquid application unit which appliesa liquid as described above to the preform body P10′.

Examples of the drying unit include a unit which supplies a heated gasor a dried gas and a vacuum unit which reduces the pressure in a spacein which the shaped article P10 is placed as described above.

Further, the shaped article production apparatus may perform at leastpart of the above-mentioned steps, and part of the above-mentioned stepsmay be performed without using the shaped article production apparatus.

Composition (Layer Forming Composition)

Next, a composition (layer forming composition) used in the embodimentsof the production method for the shaped article (three-dimensionalshaped article) mentioned above will be described in detail.

First Embodiment

Hereinafter, the layer forming composition containing particles(particle-containing composition) P1′ as described in the productionmethod and the shaped article production apparatus of the firstembodiment mentioned above will be described.

The layer forming composition (particle-containing composition) P1′contains at least a three-dimensional shaping powder containing aplurality of particles.

Three-Dimensional Shaping Powder (Particles)

Examples of a constituent material of the particles constituting thethree-dimensional shaping powder include an inorganic material, anorganic material, and a composite of these materials.

Examples of the inorganic material constituting the particles includevarious metals and metal compounds.

Examples of the metal compounds include various metal oxides such assilica, alumina, titanium oxide, zinc oxide, zirconium oxide, tin oxide,magnesium oxide, and potassium titanate; various metal hydroxides suchas magnesium hydroxide, aluminum hydroxide, and calcium hydroxide;various metal nitrides such as silicon nitride, titanium nitride, andaluminum nitride; various metal carbides such as silicon carbide andtitanium carbide; various metal sulfides such as zinc sulfide; variousmetal carbonates such as calcium carbonate and magnesium carbonate;various metal sulfates such as calcium sulfate and magnesium sulfate;various metal silicates such as calcium silicate and magnesium silicate;various metal phosphates such as calcium phosphate; various metalborates such as aluminum borate and magnesium borate; composites ofthese materials; and gypsum (various hydrates of calcium sulfate andanhydrides of calcium sulfate).

Examples of the organic material constituting the particles includesynthetic resins and natural polymers, and more specific examplesthereof include a polyethylene resin; polypropylene; polyethylene oxide;polypropylene oxide; polyethylenimine; polystyrene; polyurethane;polyurea; polyester; a silicone resin; an acrylic silicone resin; apolymer containing a (meth)acrylate ester as a constituent monomer suchas methyl polymethacrylate; a crosspolymer (an ethylene acrylic acidcopolymer resin or the like) containing a (meth)acrylate ester as aconstituent monomer such as a methyl methacrylate crosspolymer;polyamide resins such as nylon 12, nylon 6, and copolymer nylon;polyimide; cellulose; cellulose derivatives such as carboxymethylcellulose; gelatin; starch; chitin; and chitosan.

Above all, in the case where the particles are constituted by celluloseor a cellulose derivative (for example, carboxymethyl cellulose or thelike), the affinity between the particles and the cellulose derivativecontained in the composition (ink) P12 can be made more excellent, andthus, the mechanical strength, durability, and reliability of the shapedarticle P10 to be obtained finally can be made excellent. Further, whenthe composition P12 is applied to the layer P1, the layer P1 can beeffectively prevented from excessively repelling the composition P12 andthe like. As a result, the bound part (tangible part) P13 in a desiredpattern can be more reliably formed, and thus, the dimensional accuracyof the shaped article P10 can be more reliably made more excellent.

The particles constituting the three-dimensional shaping powder may besubjected to a surface treatment such as a hydrophobization treatment ora hydrophilization treatment.

The average particle diameter of the particles constituting thethree-dimensional shaping powder is not particularly limited, but ispreferably 1 μm or more and 25 μm or less, more preferably 1 μm or moreand 15 μm or less.

According to this, the mechanical strength of the shaped article P10 canbe made more excellent, and also the occurrence of undesirableirregularities or the like in the shaped article P10 to be produced ismore effectively prevented, and the dimensional accuracy of the shapedarticle P10 can be made more excellent. Further, the fluidity of thethree-dimensional shaping powder and the fluidity of the layer formingcomposition containing the three-dimensional shaping powder(particle-containing composition) P1′ can be made more excellent, andthus, the productivity of the shaped article P10 can be made moreexcellent.

The Dmax of the particles constituting the three-dimensional shapingpowder is preferably 3 μm or more and 40 μm or less, more preferably 5μm or more and 30 μm or less. According to this, the mechanical strengthof the shaped article P10 can be made more excellent, and also theoccurrence of undesirable irregularities or the like in the shapedarticle P10 to be produced is more effectively prevented, and thedimensional accuracy of the shaped article P10 can be made moreexcellent. Further, the fluidity of the three-dimensional shaping powderand the fluidity of the layer forming composition containing thethree-dimensional shaping powder (particle-containing composition) P1′can be made more excellent, and thus, the productivity of the shapedarticle P10 can be made more excellent.

The particles constituting the three-dimensional shaping powder may haveany shape, but preferably have a spherical shape. According to this, thefluidity of the three-dimensional shaping powder and the fluidity of thelayer forming composition containing the three-dimensional shapingpowder (particle-containing composition) P1′ can be made more excellent,and thus, the productivity of the shaped article P10 can be made moreexcellent, and also the occurrence of undesirable irregularities or thelike in the shaped article P10 to be produced is more effectivelyprevented, and the dimensional accuracy of the shaped article P10 can bemade more excellent.

The content of the three-dimensional shaping powder in the layer formingcomposition (particle-containing composition) P1′ is preferably 8% bymass or more and 95% by mass or less, more preferably 10% by mass ormore and 75% by mass or less. According to this, while making thefluidity of the layer forming composition (particle-containingcomposition) P1′ sufficiently excellent, the mechanical strength of theshaped article P10 to be obtained finally can be made more excellent.

Solvent

The layer forming composition P1′ may contain a volatile solvent inaddition to the components as described above.

According to this, the particles as described above can be favorablydispersed in the layer forming composition P1′, and the layer formingcomposition P1′ can be favorably formed into a paste, and thus, thefluidity of the layer forming composition P1′ can be stably madeexcellent, and the productivity of the shaped article P10 can be mademore excellent.

In the case where the layer forming composition P1′ contains a binder(which will be described later), the solvent is preferably a solventwhich dissolves the binder. According to this, the fluidity of the layerforming composition P1′ can be made favorable, and an undesirablevariation in the thickness of the layer P1 to be formed using the layerforming composition P1′ can be more effectively prevented. Further, whenthe layer P1 in a state where the solvent is removed is formed, thebinder can be adhered to the particles with higher uniformity throughoutthe entire layer P1, and thus, the occurrence of an undesirableunevenness in the composition can be more effectively prevented. Due tothis, the occurrence of an undesirable variation in the mechanicalstrength among the individual regions of the shaped article P10 to beobtained finally can be more effectively prevented, and thus, thereliability of the shaped article P10 can be further increased.

Examples of the solvent constituting the layer forming composition P1′include water; alcoholic solvents such as methanol, ethanol, andisopropanol; ketone-based solvents such as methyl ethyl ketone andacetone; glycol ether-based solvents such as ethylene glycol monoethylether and ethylene glycol monobutyl ether; glycol ether acetate-basedsolvents such as propylene glycol 1-monomethyl ether 2-acetate andpropylene glycol 1-monoethyl ether 2-acetate; polyethylene glycol, andpolypropylene glycol, and one solvent or a combination of two or moresolvents selected from these can be used.

Above all, the layer forming composition P1′ preferably contains anaqueous solvent, more preferably contains water.

According to this, the fluidity of the layer forming composition P1′ andthe uniformity of the composition of the layer P1 to be formed using thelayer forming composition P1′ can be made more excellent. Further, wateris easily removed after forming the layer P1, and also even if waterremains in the shaped article P10, water hardly causes adverse effects.In addition, water is advantageous also from the viewpoint of safety forthe human body, environmental problems, and the like. Further, in thecase where the layer forming composition P1′ contains a water-solubleresin as a binder (which will be described in detail later), thewater-soluble resin can be formed into a more favorable dissolved statein the layer forming composition P1′ , and therefore, the effect ofincluding the binder (water-soluble resin) as will be described indetail later can be more effectively exhibited.

The aqueous solvent may be any as long as it is a solvent having highsolubility in water, however, specifically, a solvent having asolubility in water (the mass of a solvent that can be dissolved in 100g of water) at 25° C. of 30 g/100 g of water or more is preferred, and asolvent having a solubility in water at 25° C. of 50 g/100 g of water ormore is more preferred.

In the case where the layer forming composition P1′ contains a solvent,the content of the solvent in the layer forming composition P1′ ispreferably 5% by mass or more and 92% by mass or less, more preferably25% by mass or more and 89% by mass or less.

According to this, the effect of including the solvent as describedabove is more remarkably exhibited, and also the solvent can be easilyremoved in a short time in the production process for the shaped articleP10, and thus, it is advantageous from the viewpoint of improvement ofthe productivity of the shaped article P10.

In particular, in the case where the layer forming composition P1′contains water as the solvent, the content of water in the layer formingcomposition P1′ is preferably 18% by mass or more and 92% by mass orless, more preferably 47% by mass or more and 90% by mass or less.

According to this, the effect as described above is more remarkablyexhibited.

In the case where the layer forming composition P1′ contains a solvent,the solvent is preferably removed from the layer forming composition P1′constituting the layer P1 before the composition P12 is applied.

According to this, the stability of the shape of the layer P1 isimproved, and also even if the solvent has low affinity for theconstituent material (for example, the cellulose derivative, the liquidcrystalline solvent, or the like) of the composition P12, undesirablerepelling of the composition P12 by the layer P1 or the like can be moreeffectively prevented, and thus, the composition P12 can be more easilyand more reliably applied in a desired pattern.

In the case where the solvent constituting the layer forming compositionP1′ is removed from the layer forming composition P1′ constituting thelayer P1 before the composition P12 is applied, the solvent may becompletely removed from the layer P1, or may be only partially removedfrom the layer P1. Even in such a case, the effect as described above isexhibited.

Binder

The layer forming composition P1′ may contain a binder.

According to this, a plurality of particles can be favorably bound(temporarily fixed) to one another in the layer P1 formed using thelayer forming composition P1′ (particularly the layer P1 in a statewhere the solvent is removed), and thus, undesirable scattering or thelike of the particles can be effectively prevented. As a result, thesafety for workers and the dimensional accuracy of the shaped articleP10 to be produced can be further improved.

In the case where the layer forming composition P1′ contains a binder,the binder is preferably dissolved in a solvent in the layer formingcomposition P1′.

According to this, the fluidity of the layer forming composition P1′ canbe made more favorable, and an undesirable variation in the thickness ofthe layer P1 to be formed using the layer forming composition P1′ can bemore effectively prevented. Further, when the layer P1 in a state wherethe solvent is removed is formed, the binder can be adhered to theparticles with higher uniformity throughout the entire layer P1, andthus, the occurrence of an undesirable unevenness in the composition canbe more effectively prevented. Due to this, the occurrence of anundesirable variation in the mechanical strength among the individualregions of the shaped article P10 to be obtained finally can be moreeffectively prevented, and thus, the reliability of the shaped articleP10 can be further increased.

The binder may be any as long as it has a function to temporarily fix aplurality of particles in the layer P1 formed using the layer formingcomposition P1′ (particularly the layer P1 in a state where the solventis removed), however, a water-soluble resin can be favorably used.

By including a water-soluble resin, in the case where the layer formingcomposition P1′ contains an aqueous solvent (particularly water) as thesolvent, the binder (water-soluble resin) can be included in the layerforming composition P1′ in a dissolved state, and thus, the fluidity andhandleability (ease of handling) of the layer forming composition P1′can be made more excellent. As a result, the productivity of the shapedarticle P10 can be made more excellent.

Further, a region of the layer P1 to which the composition P12 is notapplied in the production process for the shaped article P10 can beeasily and efficiently removed by applying an aqueous solvent(particularly water) thereto. As a result, the productivity of theshaped article P10 can be made more excellent. Further, the region ofthe layer which should be removed can be easily and reliably preventedfrom adhering to or remaining in the finally obtained shaped articleP10, and thus, the dimensional accuracy of the shaped article P10 can bemade more excellent.

Hereinafter, the water-soluble resin as the binder will be mainlydescribed.

The water-soluble resin may be any as long as it can be at leastpartially dissolved in an aqueous solvent, but is preferably, forexample, a resin having a solubility in water (the mass of a resin thatcan be dissolved in 100 g of water) at 25° C. of 5 g/100 g of water ormore, more preferably a resin having a solubility in water at 25° C. of10 g/100 g of water or more.

Examples of the water-soluble resin include synthetic polymers such aspolyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polycaprolactonediol, sodium polyacrylate, ammonium polyacrylate, polyacrylamide,modified polyamide, polyethylenimine, polyethylene oxide, and a randomcopolymer of ethylene oxide and propylene oxide; natural polymers suchas corn starch, mannan, pectin, agar, alginic acid, dextran, glue, andgelatin; and semisynthetic polymers such as carboxymethyl cellulose,hydroxyethyl cellulose, starch, oxidized starch, and modified starch,and one material or a combination of two or more materials selected fromthese can be used.

Above all, in the case where the water-soluble resin as the binder ispolyvinyl alcohol, the mechanical strength of the shaped article P10 canbe made more excellent. Further, by adjusting the saponification degreeor the polymerization degree, the properties (for example, watersolubility, water resistance, etc.) of the binder and the properties(for example, viscosity, the ability to fix the particles, wettability,etc.) of the layer forming composition P1′ can be more favorablycontrolled. Due to this, polyvinyl alcohol can be more favorably appliedto the production of a variety of shaped articles P10. Further,polyvinyl alcohol is inexpensive and offers a stable supply among thevarious water-soluble resins. Due to this, while keeping the productioncost low, the shaped article P10 can be stably produced.

In the case where the water-soluble resin as the binder containspolyvinyl alcohol, the saponification degree of the polyvinyl alcohol ispreferably 85 or more and 90 or less. According to this, a decrease inthe solubility of polyvinyl alcohol in an aqueous solvent (particularlywater) can be prevented. Due to this, in the case where the layerforming composition P1′ contains an aqueous solvent (particularlywater), a decrease in the adhesiveness between adjacent layers P1 can bemore effectively prevented.

In the case where the water-soluble resin as the binder containspolyvinyl alcohol, the polymerization degree of the polyvinyl alcohol ispreferably 300 or more and 1,000 or less. According to this, in the casewhere the layer forming composition P1′ contains an aqueous solvent(particularly water), the mechanical strength of the respective layersP1 and the adhesiveness between adjacent layers P1 can be made moreexcellent.

Further, in the case where the water-soluble resin as the binder ispolyvinylpyrrolidone (PVP), effects as described below are obtained.That is, polyvinylpyrrolidone has excellent adhesiveness to variousmaterials such as a glass, a metal, and a plastic, and therefore, thestrength and the stability of the shape of a portion of the layer P1 towhich the composition P12 is not applied can be made more excellent, andthe dimensional accuracy of the shaped article P10 to be obtainedfinally can be made more excellent. Further, polyvinylpyrrolidone showshigh solubility in water, and therefore, in an unbound particle removalstep (after completion of shaping), among the particles constituting therespective layers P1, the particles which are not bound to one anotherby the reaction product of the liquid crystalline solvent or the likecan be easily and reliably removed. Further, polyvinylpyrrolidone hasmoderate affinity for the three-dimensional shaping powder as describedabove, and therefore has relatively high wettability to the surfaces ofthe particles. Due to this, the function to temporarily fix theparticles as described above can be more effectively exhibited. Further,polyvinylpyrrolidone has excellent affinity for various coloring agents,and therefore, in the case where the composition P12 containing acoloring agent is used in the composition application step (inkapplication step), undesirable diffusion of the coloring agent can beeffectively prevented. Further, in the case where the layer formingcomposition P1′ in the form of a paste contains polyvinylpyrrolidone,the inclusion of a bubble in the layer forming composition P1′ can beeffectively prevented, and in the layer forming step, the occurrence ofa defect due to the inclusion of a bubble can be more effectivelyprevented.

In the case where the water-soluble resin as the binder containspolyvinylpyrrolidone, the weight average molecular weight of thepolyvinylpyrrolidone is preferably 10,000 or more 1,700,000 or less,more preferably 30,000 or more 1,500,000 or less.

According to this, the above-mentioned function can be more effectivelyexhibited.

Further, in the case where the water-soluble resin is polycaprolactonediol, the layer forming composition P1′ can be favorably formed intopellets, and undesirable scattering or the like of the particles can bemore effectively prevented, and the handleability (ease of handling) ofthe layer forming composition P1′ is improved, so that the safety forworkers and the dimensional accuracy of the shaped article P10 to beproduced can be improved. Further, melting can be achieved at arelatively low temperature, and thus, the energy and cost required forthe production of the shaped article P10 can be kept low, and also theproductivity of the shaped article P10 can be made sufficientlyexcellent.

In the case where the water-soluble resin as the binder containspolycaprolactone diol, the weight average molecular weight of thepolycaprolactone diol is preferably 10,000 or more 1,700,000 or less,more preferably 30,000 or more 1,500,000 or less.

According to this, the above-mentioned function can be more effectivelyexhibited.

In the layer forming composition P1′, the binder is preferably in aliquid state (for example, in a dissolved state, in a molten state, orthe like) in the layer forming step.

According to this, the uniformity of the thickness of the layer P1 to beformed using the layer forming composition P1′ can be easily andreliably further increased.

In the case where the layer forming composition P1′ contains a binder,the content of the binder in the layer forming composition P1′ ispreferably 0.5% by mass or more and 25% by mass or less, more preferably1.0% by mass or more and 10% by mass or less.

According to this, the effect of including the binder as described aboveis more remarkably exhibited, and also the content of the particles andthe like in the layer forming composition P1′ can be made sufficientlyhigh, and thus, the mechanical strength and the like of the shapedarticle P10 to be produced can be made more excellent.

Other Component

The layer forming composition P1′ may contain a component other than theabove-mentioned components. Examples of such a component include apolymerization initiator, a polymerization accelerator, a crosslinkingagent, a siloxane compound, a permeation accelerator, a wetting agent(humectant), a fixing agent, an antifungal agent, a preservative, anantioxidant, a UV absorber, a chelating agent, and a pH adjusting agent.

Second Embodiment

Hereinafter, the layer forming composition (the composition to beejected by an inkjet method) as described in the production method andthe shaped article production apparatus of the second embodimentmentioned above will be described.

In this embodiment, as the composition, a tangible part forming ink P16′and a support part forming ink P17′ are used.

The tangible part forming ink P16′ has been described in detail as thecomposition containing a cellulose derivative and a liquid crystallinesolvent, and therefore, hereinafter, the support part forming ink P17′will be described in detail.

Support Part Forming Ink

The support part forming ink P17′ contains at least a curable resin(curable component).

Curable Resin

Examples of the curable resin (curable component) constituting thesupport part forming ink P17′ include the same curable resins (curablecomponents) as those exemplified as the constituent component (anothercurable component) of the tangible part forming ink P16′.

In particular, it is preferred that the curable resin (curablecomponent) constituting the support part forming ink P17′ and thecurable component (another curable component) constituting the tangiblepart forming ink P16′ described above are cured by the same type ofenergy ray.

According to this, the structure of the production apparatus to be usedfor producing the shaped article can be effectively prevented from beingcomplicated, and thus, the productivity of the shaped article P10 can bemade more excellent. Further, the surface shape of the shaped articleP10 can be more reliably controlled.

The support part forming ink P17′ preferably contains one or morecurable components particularly selected from the group consisting oftetrahydrofurfuryl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate,polyethylene glycol di(meth)acrylate, and (meth)acryloyl morpholineamong various curable components.

According to this, while more reliably making the appearance of theshaped article P10 excellent, the productivity of the shaped article P10can be made more excellent.

Further, the mechanical strength and the stability of the shape of thesupport part P17 to be formed by curing the support part forming inkP17′ can be made more excellent. As a result, when producing the shapedarticle P10, the support part P17 in the lower layer (first layer) canmore favorably support the tangible part forming ink P16′ for formingthe upper layer (second layer). Due to this, undesirable deformation(particularly, sagging or the like) of the tangible part P16 can be morefavorably prevented, and thus, the dimensional accuracy of the shapedarticle P10 to be obtained finally can be made further more excellent.

In particular, when the support part forming ink P17′ contains(meth)acryloyl morpholine, an effect as described below is obtained.

That is, when (meth)acryloyl morpholine is in an incompletely curedstate even if a curing reaction has proceeded (a polymer of(meth)acryloyl morpholine in an incompletely cured state),(meth)acryloyl morpholine is in a state where the solubility in varioussolvents such as water is high. Therefore, in the support sectionremoval step as described above, while more effectively preventing theoccurrence of a defect in the tangible part P16, the support part P17can be selectively and reliably, and also efficiently removed. As aresult, the shaped article P10 having a desired form can be obtainedwith high productivity and higher reliability.

Further, when the support part forming ink P17′ containstetrahydrofurfuryl (meth)acrylate, the flexibility after curing can bemaintained more favorably, and in a treatment with a liquid for removingthe support part P17, the support part P17 is more easily formed into agel, and therefore, the efficiency of removal of the support part P17can be further enhanced.

Further, when the support part forming ink P17′ containsethoxyethoxyethyl (meth) acrylate, in a treatment with a liquid forremoving the support part P17, the efficiency of removal of the supportpart P17 can be enhanced.

Further, when the support part forming ink P17′ contains polyethyleneglycol di (meth) acrylate, in the case where a liquid for removing thesupport part P17 contains water as a main component, the solubility ofthe support part P17 in the liquid is increased, and thus, the supportpart P17 can be more easily removed.

The content of the curable component in the support part forming inkP17′ is preferably 83% by mass or more and 98.5% by mass or less, morepreferably 87% by mass or more and 95.4% by mass or less.

According to this, the stability of the shape of the support part P17 tobe formed can be made more excellent, and in the case where the layersP1 are stacked when producing the shaped article P10, undesirabledeformation of the layer P1 on the lower side can be more effectivelyprevented, and the layer P1 on the upper side can be favorablysupported. As a result, the dimensional accuracy of the shaped articleP10 to be obtained finally can be made more excellent. Further, theproductivity of the shaped article P10 can be made more excellent.

Polymerization Initiator

The support part forming ink P17′ preferably contains a polymerizationinitiator.

According to this, the curing speed of the support part forming ink P17′when producing the shaped article P10 can be moderately increased, andthus, the productivity of the shaped article P10 can be made moreexcellent.

Further, the stability of the shape of the support part P17 to be formedcan be made more excellent, and in the case where the layers P1 arestacked when producing the shaped article P10, undesirable deformationof the layer P1 on the lower side can be more effectively prevented, andthe layer P1 on the upper side can be favorably supported. As a result,the dimensional accuracy of the shaped article P10 to be obtainedfinally can be made more excellent.

Examples of the polymerization initiator constituting the support partforming ink P17′ include the same polymerization initiators as thoseexemplified as the constituent component of the tangible part formingink P16′.

In particular, the support part forming ink P17′ preferably contains atleast one of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide as the polymerizationinitiator.

By including such a polymerization initiator, while more reliably makingthe properties of the surface of the tangible part P16 (the tangiblepart P16 to be formed using the tangible part forming ink P16′) which isformed in contact with the support part P17 (the support part P17 to beformed using the support part forming ink P17′) favorable, and alsowhile more reliably making the appearance of the shaped article P10excellent, the productivity of the shaped article P10 can be made moreexcellent.

In addition, the mechanical strength and the stability of the shape ofthe support part P17 to be formed by curing the support part forming inkP17′can be made more excellent. As a result, when producing the shapedarticle P10, the support part P17 in the lower layer (first layer) canmore favorably support the tangible part forming ink P16′ for formingthe upper layer (second layer). Due to this, undesirable deformation(particularly, sagging or the like) of the tangible part P16 can be morefavorably prevented, and thus, the dimensional accuracy of the shapedarticle P10 to be obtained finally can be made further more excellent.

A specific value of the content of the polymerization initiator in thesupport part forming ink P17′ is preferably 1.5% by mass or more and 17%by mass or less, more preferably 4.6% by mass or more and 13% by mass orless.

According to this, while more reliably making the appearance of theshaped article P10 excellent, the productivity of the shaped article P10can be made more excellent.

Further, the mechanical strength and the stability of the shape of thesupport part P17 to be formed by curing the support part forming inkP17′ can be made more excellent. As a result, when producing the shapedarticle P10, the support part P17 in the lower layer (first layer) canmore favorably support the tangible part forming ink P16′ for formingthe upper layer (second layer). Due to this, undesirable deformation(particularly, sagging or the like) of the tangible part P16 can be morefavorably prevented, and thus, the dimensional accuracy of the shapedarticle P10 to be obtained finally can be made further more excellent.

Other Component

The support part forming ink P17′ may contain a component other than theabove-mentioned components. Examples of such a component include variouscoloring agents such as a pigment and a dye, a dispersant, a surfactant,a sensitizer, a polymerization accelerator, a solvent, a permeationaccelerator, a wetting agent (humectant), a fixing agent, an antifungalagent, a preservative, an antioxidant, a UV absorber, a chelating agent,a pH adjusting agent, a thickening agent, a filler, an anti-aggregationagent, and a defoaming agent.

In particular, by including a coloring agent in the support part formingink P17′, the visibility of the support part P17 is improved, and in theshaped article P10 to be obtained finally, at least a portion of thesupport part P17 can be more reliably prevented from undesirablyremaining.

Examples of the coloring agent constituting the support part forming inkP17′ include the same coloring agents as those exemplified as theconstituent component of the tangible part forming ink P16′, however,the coloring agent is preferably a coloring agent which gives a colordifferent from the color of the tangible part P16 (a color of the shapedarticle P10 to be visually recognized in appearance) superimposed on thesupport part P17 formed using the support part forming ink P17′ whenobserved from the normal direction of the surface of the shaped articleP10. According to this, the effect as described above is more remarkablyexhibited.

In the case where the support part forming ink P17′ contains a pigment,if the support part forming ink P17′ further contains a dispersant, thedispersibility of the pigment can be made more favorable. Examples ofthe dispersant constituting the support part forming ink P17′ includethe same dispersants as those exemplified as the constituent componentof the tangible part forming ink P16′.

The viscosity of the support part forming ink P17′ in the inkapplication step is preferably 2 mPa·s or more and 30 mPa·s or less,more preferably 5 mPa·s or more and 20 mPa·s or less.

According to this, the ejection stability of the support part formingink P17′ by an inkjet method can be made more excellent.

In the production of the shaped article P10, a plurality of types ofsupport part forming inks P17′ may be used.

Hereinabove, preferred embodiments of the invention have been described,however, the invention is not limited thereto.

For example, in the above-mentioned embodiments, a case where a squeegeeis used as the flattening unit has been mainly described, however, aroller or the like may be used in place of the squeegee.

Further, the production apparatus to be used for producing the shapedarticle according to the invention may include a recovery mechanism (notshown) for recovering the composition which is not used for forming thelayer in the composition supplied from the composition supply section.According to this, while preventing the accumulation of the excesscomposition in a region where the layer is formed, a sufficient amountof the composition can be supplied, and therefore, while moreeffectively preventing the occurrence of a defect in the layer, theshaped article can be produced more stably. Further, the recoveredcomposition can be used for producing the shaped article again, andtherefore, this can contribute to the reduction in the production costof the shaped article, so that this configuration is preferred also fromthe viewpoint of resource saving.

Further, the production apparatus to be used for producing the shapedarticle according to the invention may include a recovery mechanism forrecovering the composition removed in the unbound particle removal step.

Further, in the above-mentioned embodiments, a case where the tangiblepart is formed in all the layers has been described, however, a layer inwhich the tangible part is not formed may be formed. For example, thetangible part is not formed in a layer formed immediately above thestage, and the layer may be made to function as a sacrifice layer.

Further, in the above-mentioned embodiments, a case where the inkapplication step is performed by an inkjet method has been mainlydescribed, however, the ink application step may be performed usinganother method (for example, another printing method).

Further, the tangible part forming ink and the support part forming inkmaybe applied by a method other than the inkjet method (for example,another printing method).

Further, in the above-mentioned embodiments, a case where in addition tothe layer forming step and the composition application step (inkapplication step), the solidification step is also performed repeatedlyalong with the layer forming step and the ink application step has beendescribed, however, the solidification step may not be performedrepeatedly. For example, after forming a stacked body including aplurality of layers which have not been subjected to a solidificationtreatment for solidifying the composition in the form of a liquid, theplurality of layers are subjected to the solidification treatment alltogether. According to this, for example, a treatment of applying anenergy for solidifying (curing) the composition in the form of a liquidcan be reduced, and therefore, even in the case of using a materialhaving low resistance to the energy in the production of the shapedarticle, undesirable denaturation, deterioration, or the like byapplication of the energy can be effectively prevented.

Further, in the above-mentioned embodiments, a case where a chemicalreaction involving the reactive functional group of the liquidcrystalline solvent constituting the composition is allowed to proceedafter supplying the composition according to the invention to a givenregion has been described, however, the chemical reaction involving thereactive functional group of the liquid crystalline solvent may beallowed to proceed partially before supplying the composition to a givenregion.

In the invention, it is only necessary to use the composition containingthe cellulose derivative having a liquid crystalline functional groupand the liquid crystalline solvent having a reactive functional groupfor forming at least a portion of the tangible part of the shapedarticle, and the tangible part may have a portion which is formedwithout using the composition.

Further, in the production of the shaped article according to theinvention, a pre-treatment step, an intermediate treatment step, or apost-treatment step may be performed as needed.

Examples of the pre-treatment step include a stage cleaning step.

As the intermediate treatment step, for example, in the case where thelayer forming composition is in the form of pellets, a step of stoppingheating or the like (binder solidification step) may be included betweenthe layer forming step and the composition application step (inkapplication step). According to this, the binder constituting thepellets is formed into a solid state, and the layer can be obtained as alayer in which the binding force between the particles is higher.Further, for example, in the case where the layer forming compositioncontains a solvent component (dispersion medium) such as water, asolvent component removal step in which the solvent component is removedmay be included between the layer forming step and the compositionapplication step (ink application step). According to this, the layerforming step can be performed more smoothly, and an undesirablevariation in the thickness of the layer to be formed can be moreeffectively prevented. As a result, the shaped article having higherdimensional accuracy can be produced with higher productivity.

Examples of the post-treatment step include a washing step, a shapeadjustment step in which deburring or the like is performed, a coloringstep, and a coating layer forming step.

Further, in the above-mentioned embodiments, a case where the flatteningunit moves on the stage has been described, however, the flattening maybe performed by moving the stage so as to change the positionalrelationship between the stage and the squeegee.

Further, the shaped article production apparatus may include a heatingunit for heating the composition containing the cellulose derivativehaving a liquid crystalline functional group and the liquid crystallinesolvent having a reactive functional group or a heating unit for heatinga region to which the composition containing the cellulose derivativehaving a liquid crystalline functional group and the liquid crystallinesolvent having a reactive functional group is applied.

Further, in the above-mentioned embodiments, a case where the shapedarticle production apparatus includes an energy ray irradiation unitwhich irradiates an energy ray as the solidification unit has beenrepresentatively described, however, the solidification unit included inthe shaped article production apparatus maybe another unit such as aheating unit.

Further, the shaped article according to the invention may not be ashaped article produced using the above-mentioned method or apparatus.

Further, in the above-mentioned embodiments, in the case where thecellulose derivative is a cellulose derivative having a reactivefunctional group which reacts with a siloxane compound, a crosslinkingagent, or the like, or in the case where the liquid crystalline solventis a liquid crystalline solvent which reacts with a siloxane compound, acrosslinking agent, or the like, a case where a reactive component suchas a siloxane compound or a crosslinking agent is contained in thecomposition (the composition containing the cellulose derivative havinga liquid crystalline functional group and the liquid crystalline solventhaving a reactive functional group) according to the invention has beenmainly described, however, the reaction component may not be containedin the composition according to the invention, and for example, thereaction component may be a reaction component which comes in contactwith the cellulose derivative or the liquid crystalline solvent when itreacts with the cellulose derivative or the liquid crystalline solvent.

Further, when the shaped article according to the invention is produced,a chemical reaction other than the above-mentioned chemical reaction maybe performed. For example, in the case where the composition accordingto the invention contains a cellulose derivative having an acetylatedhydroxy group, a reaction to release the acetyl group (deacetylationreaction) may be performed in the production of the shaped article.According to this, for example, in the composition, while making thehydrophobicity of the cellulose derivative higher, the hydrophobicity ofthe shaped article to be obtained finally can be made relatively low,and thus, the properties of the shaped article can be made compatiblewith the productivity of the shaped article and the storage stability ofthe composition.

EXAMPLES

Hereinafter, the invention will be described in more detail withreference to specific Examples, however, the invention is not limitedonly to these Examples. In the following description, a treatment inwhich the temperature condition is not particularly shown was performedat room temperature (25° C.). Further, for various measurementconditions in which the temperature condition is not particularly shown,values at room temperature (25° C.) are shown.

(1) Production of Three-Dimensional Shaped Article Example 1 1.Preparation of Material (Composition) to be Used for Production ofThree-Dimensional Shaped Article 1-1. Preparation of Layer FormingComposition

First, a powder constituted by silica particles having an averageparticle diameter of 2.6 μm and a Dmax of 10 μm was prepared.

Subsequently, the powder (30.00 mass %), water (60.00 mass %), andammonium polyacrylate (10.00 mass %) as a water-soluble resin weremixed, whereby a layer forming composition was obtained.

1-2. Preparation of Composition in the Form of Liquid (Ink)

Cellulose (10 g) was dissolved in a mixture of THF (200 mL) and pyridine(10 mL), and the resulting mixture was stirred well. To the mixture, asolution in which 2-bromo-2-methylpropionyl bromide (7 mL) was dissolvedin THF (10 mL) was added dropwise at 0° C. over 1 hour. After completionof dropwise addition, the mixture was heated to 45° C. After heating themixture for about 20 hours, the reaction mixture was added to a largeamount of methanol. The deposited solid was filtered, dissolved inacetone, and then, reprecipitated in methanol. This procedure wasrepeated 3 times, and the obtained solid was dried in vacuo overnight,whereby a compound represented by the following formula (21) wasobtained.

After the compound (1 g) represented by the above formula (21) wasdissolved in N-methylpyrrolidone (NMP) (400 mL), allylamine (10 g) wasadded thereto, and thereafter, a compound (0.8 g) which has an ionicmoiety and is represented by the following formula (22) was furtheradded thereto.

In the formula (22), k is 8.

Separately, a solution in which CuBr (0.13 g) andpentamethyldiethylenetriamine (PMDETA) (0.4 mL) were dissolved in NMP(15 mL) was prepared, and this solution was added to a solutioncontaining the compound represented by the above formula (21) preparedas described above and the compound represented by the above formula(22), and the resulting mixture was heated and stirred at 75° C. for 12hours.

In this manner, a compound represented by the following formula (23) wassynthesized.

In the formula (23), R^(l) is a substituent represented by the formula(9) in which k is 8 and R⁷ is a methyl group.

Thereafter, to the above reaction mixture, a compound (a compound whichis in the form of a liquid and has a liquid crystalline functionalgroup) represented by the following formula (24) was added in an amountcorresponding to a desired introduction amount, and the resultingmixture was heated and stirred at 75° C. for 12 hours.

In the formula (24), j is 8.

Subsequently, to this reaction mixture, an NMP solution (10 mL) oftributyltin hydride (1 mL) was added, and the resulting mixture wasfurther heated for 1 hour. Thereafter, the flask was uncapped, andoxygen was introduced into the flask to stop the reaction. The reactionmixture was diluted with 200 mL of acetone and passed through an aluminacolumn to remove the catalyst. The resulting solution was added to 10mass % hydrochloric acid, and the resulting solid was filtered,dissolved in acetone, reprecipitated in methanol, and then, dried invacuo, whereby a cellulose derivative which has a liquid crystallinefunctional group and an ionic moiety as a chemical structure in commonwith an ionic liquid and is represented by the following formula (25)was obtained.

In the formula (25), R^(l) is a substituent represented by the formula(9) in which k is 8 and R⁷ is a methyl group. In the formula (25), R² isa substituent represented by the formula (10) in which j is 8.

The cellulose derivative (48 parts by mass) represented by the aboveformula (25) obtained as described above, the liquid crystalline solvent(50 parts by mass) represented by the above formula (24), andbis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (2 parts by mass) as apolymerization initiator were mixed, whereby a composition in the formof a liquid (ink) was obtained.

2. Production of Three-Dimensional Shaped Article

By using the layer forming composition and the ink obtained as describedabove, a three-dimensional shaped article A having a shape as shown inFIG. 5, that is, having a thickness of 4 mm and a length of 150 mm, andhaving regions, which are provided on both ends (on the upper and lowersides in the drawing), respectively, shown by the shaded portions, andeach have a width of 20 mm and a length of 35 mm, and also having aregion, which is sandwiched between these regions and has a width of 10mm and a length of 80 mm, and a three-dimensional shaped article Bhaving a shape as shown in FIG. 6, that is, having a rectangularparallelepiped shape with a thickness of 4 mm, a width of 10 mm, and alength of 80 mm were produced as follows.

First, a shaped article production apparatus as shown in FIG. 3 wasprepared, and on the surface of the support body (stage), a layer havinga thickness of 50 lam was formed by a squeegee method using the layerforming composition (layer forming step). As the stage of the shapedarticle production apparatus, a stage having a surface constituted bypolyimide subjected to an alignment treatment by a rubbing treatment wasused.

Subsequently, after forming the layer, the layer was heated to 150° C.and left for 2 minutes, whereby water contained in the layer formingcomposition was removed.

Subsequently, to the layer from which water was removed, the compositionin the form of a liquid (ink) containing the cellulose derivative havinga liquid crystalline functional group and the liquid crystalline solventhaving a reactive functional group was applied in a given pattern by aninkjet method (composition application step). In this step, thecomposition (ink) previously heated to 85° C. or higher was ejected.Further, in this step, prior to the application of the composition(ink), a region to which the composition (ink) was to be applied waspreviously heated to 85° C. or higher.

Subsequently, the layer was irradiated with a UV light to allow apolymerization reaction (curing reaction) of the liquid crystallinesolvent contained in the layer to proceed, thereby curing the solvent(solidification step).

Thereafter, a series of steps from the layer forming step to the curingstep were performed repeatedly so as to stack a plurality of layerswhile changing the application pattern of the ink in accordance with theshape of a three-dimensional shaped article to be produced.

Thereafter, the stacked body obtained as described above was immersed inwater, and ultrasonic vibration was applied thereto to remove theparticles which were not bound to one another (unbound particles) by thesolidified material (cured material) of the ink among the particlesconstituting the respective layers (unbound particle removal step). Inthis manner, two three-dimensional shaped articles A and twothree-dimensional shaped articles B were obtained.

Examples 2 to 7

Inks (compositions in the form of a liquid) and three-dimensional shapedarticles were produced in the same manner as in the above Example 1except that the types of raw materials to be used for the preparation ofthe ink (the composition in the form of a liquid), and the compositionalratios of the respective components were changed as shown in Table 1.

Example 8

First, as curing components, acryloyl morpholine, tetrahydrofurfurylacrylate, ethoxyethoxyethyl acrylate, and polyethylene glycol diacrylatewere used, as a polymerization initiator,2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide was used, and thesecompounds were mixed with one another, whereby a support part formingink was obtained.

On the other hand, a cellulose derivative prepared in the same manner asdescribed in Example 1 was mixed with the liquid crystalline solvent andthe polymerization initiator, whereby a tangible part forming ink wasprepared.

Then, by using the support part forming ink and the tangible partforming ink, a three-dimensional shaped article A having a shape asshown in FIG. 5, that is, having a thickness of 4 mm and a length of 150mm, and having regions, which are provided on both ends (on the upperand lower sides in the drawing), respectively, shown by the shadedportions, and each have a width of 20 mm and a length of 35 mm, and alsohaving a region, which is sandwiched between these regions and has awidth of 10 mm and a length of 80 mm, and a three-dimensional shapedarticle B having a shape as shown in FIG. 6, that is, having arectangular parallelepiped shape with a thickness of 4 mm, a width of 10mm, and a length of 80 mm were produced as follows.

First, a shaped article production apparatus as shown in FIG. 4 wasprepared, and onto the surface of the support body (stage), the tangiblepart forming ink and the support part forming ink were ejected in agiven pattern by an inkjet method (ink application step), andthereafter, a UV light was irradiated thereon, whereby these inks werecured (curing step). In the ink application step, the respective inkswere ejected so that the peripheral portion of the tangible part formingink comes in contact with the support part forming ink. Further, in theink application step, the composition (ink) previously heated to 85° C.or higher was ejected. Further, in the ink application step, prior tothe application of the composition (ink), a region to which thecomposition (ink) was to be applied was previously heated to 85° C. orhigher.

The thickness of the layer formed using the support part forming ink inthe peripheral portion of the tangible part forming ink was 50 lam.Incidentally, as the stage of the shaped article production apparatus, astage having a surface constituted by polyimide subjected to analignment treatment by a rubbing treatment was used.

Thereafter, a series of steps from the layer forming step to the curingstep were performed repeatedly so as to stack a plurality of layerswhile changing the application pattern of the ink in accordance with theshape of a three-dimensional shaped article to be produced, whereby apreform body was obtained.

Thereafter, the preform body obtained as described above was immersed inan organic solvent in which the ink before light irradiation wasdissolved, and ultrasonic vibration was applied thereto to selectivelyremove the support part (support part removal step). In this manner, twothree-dimensional shaped articles A and two three-dimensional shapedarticles B were obtained.

Examples 9 to 14

Tangible part forming inks (compositions in the form of a liquid) andthree-dimensional shaped articles were produced in the same manner as inthe above Example 8 except that the types of raw materials to be usedfor the preparation of the tangible part forming ink, and thecompositional ratios of the respective components were changed as shownin Table 1.

Comparative Example 1

A tangible part forming ink (a composition in the form of a liquid) anda three-dimensional shaped article were produced in the same manner asin the above Example 8 except that a compound represented by thefollowing formula (34) was used as a compound which does not have aliquid crystalline functional group in place of the liquid crystallinesolvent, and also the contents of the respective components wereadjusted.

Comparative Example 2

A tangible part forming ink (a composition in the form of a liquid) anda three-dimensional shaped article were produced in the same manner asin the above Example 8 except that a compound represented by thefollowing formula (35) was used as a compound which does not have areactive functional group in place of the liquid crystalline solvent,and also the contents of the respective components were adjusted.

Comparative Example 3

A tangible part forming ink (a composition in the form of a liquid) anda three-dimensional shaped article were produced in the same manner asin the above Example 8 except that a compound represented by thefollowing formula (30) which does not have a liquid crystallinefunctional group was used as the cellulose derivative, and also thecontents of the respective components were adjusted.

In the formula (30), R¹ is a substituent represented by the formula (9)in which k is 8 and R⁷ is a methyl group.

Comparative Example 4

A tangible part forming ink (a composition in the form of a liquid) anda three-dimensional shaped article were produced in the same manner asin the above Example 8 except that cellulose was used in place of thecellulose derivative, and also the contents of the respective componentswere adjusted.

The formulations of the compositions in the form of a liquid (the inksin the case of Examples 1 to 7, and the tangible part forming inks inthe case of Examples 8 to 14) used in the above respective Examples andComparative Examples are shown in Table 1. In the table, a compoundwhich is a cellulose derivative represented by the above formula (25) inwhich R^(l) is a substituent represented by the formula (9) in which kis 8 and R⁷ is a methyl group, and R² is a substituent represented bythe formula (10) in which j is 8 is denoted by “CD25A”; a compound whichis a cellulose derivative represented by the above formula (25) in whichR¹ is a substituent represented by the formula (9) in which k is 10 andR⁷ is a methyl group, and R² is a substituent represented by the formula(11) in which j is 10 and R⁶ is a butoxy group is denoted by “CD25B”; acompound which is a cellulose derivative represented by the followingformula (26) in which R² is a substituent represented by the formula(10) in which j is 12 is denoted by “CD26A”; a compound which is acellulose derivative represented by the following formula (26) in whichR² is a substituent represented by the formula (11) in which j is 12 andR⁶ is a butoxy group is denoted by “CD26B”; a compound which is acellulose derivative represented by the above formula (30) in which R¹is a substituent represented by the formula (9) in which k is 8 and R⁷is a methyl group is denoted by “CD30”; a compound which is a liquidcrystalline solvent represented by the above formula (24) in which j is8 is denoted by “SLC24”; a compound which is a liquid crystallinesolvent represented by the following formula (31) in which j is 12 isdenoted by “SLC31”; a compound represented by the above formula (34) isdenoted by “C34”; a compound represented by the above formula (35) isdenoted by “C35”; and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxideis denoted by “I1”. Further, in the above respective Examples, theviscosity of the ink when the ink was ejected by an inkjet method waswithin the range of 5 mPa·s or more and 20 mPa·s or less in all cases.Further, in the above respective Examples, the temperature of the inkwhen the ink was ejected was within the range of 35° C. or higher and75° C. or lower in all cases. Further, in the above respective Examples,the temperature of the region to which the ink was applied when the inkwas ejected was previously adjusted within the range of 35° C. or higherand 75° C. or lower in all cases.

TABLE 1 Cellulose Liquid crystalline Polymerization Other derivativesolvent initiator component Content Content Content Content [parts by[parts by [parts by [parts by type mass] type mass] type mass] typemass] Example 1 CD25A 48 SLC24 50 I1 2 — — Example 2 CD26A 48 SLC24 50I1 2 — — Example 3 CD25B 48 SLC31 50 I1 2 — — Example 4 CD26B 48 SLC3150 I1 2 — — Example 5 CD25A 48 SLC31 50 I1 2 — — Example 6 CD26A 48SLC31 50 I1 2 — — Example 7 CD25B 48 SLC24 50 I1 2 — — Example 8 CD25A28 SLC24 70 I1 2 — — Example 9 CD26A 28 SLC24 70 I1 2 — — Example 10CD25B 28 SLC31 70 I1 2 — — Example 11 CD26B 28 SLC31 70 I1 2 — — Example12 CD25A 28 SLC31 70 I1 2 — — Example 13 CD26A 28 SLC31 70 I1 2 — —Example 14 CD25B 28 SLC24 70 I1 2 — — Comparative CD25A 48 — — I1 2 C3450 Example 1 Comparative CD25A 48 — — I1 2 C35 50 Example 2 Comparative— — SLC24 48 I1 2 CD30 50 Example 3 Comparative — — SLC24 48 I1 2cellulose 50 Example 4

2 Evaluation 2.1 Dimensional Accuracy

With respect to the three-dimensional shaped articles B of the aboverespective Examples and Comparative Examples, the thickness, width, andlength were measured, and the deviation amount from the set value wasdetermined and evaluated according to the following criteria.

A: The deviation amount from the set value which is the largest of thedeviation amounts from the set values for the thickness, width, andlength is less than 1.0%.

B: The deviation amount from the set value which is the largest of thedeviation amounts from the set values for the thickness, width, andlength is 1.0% or more and less than 2.0%.

C: The deviation amount from the set value which is the largest of thedeviation amounts from the set values for the thickness, width, andlength is 2.0% or more and less than 4.0%.

D: The deviation amount from the set value which is the largest of thedeviation amounts from the set values for the thickness, width, andlength is 4.0% or more and less than 7.0%.

E: The deviation amount from the set value which is the largest of thedeviation amounts from the set values for the thickness, width, andlength is 7.0% or more.

2.2 Tensile Strength

With respect to the three-dimensional shaped articles A of the aboverespective Examples and Comparative Examples, the tensile strength wasmeasured under the conditions that the tensile yield stress was 50mm/min and the tensile modulus of elasticity was 1 mm/min according toJIS K 7161:1994 (ISO 527:1993) and evaluated according to the followingcriteria.

A: The tensile strength is 100 MPa or more.

B: The tensile strength is 10 MPa or more and less than 100 MPa.

C: The tensile strength is 1 MPa or more and less than 10 MPa.

D: The tensile strength is less than 1 MPa.

These results are summarized in Table 2.

TABLE 2 Dimensional accuracy Tensile strength Example 1 A A Example 2 AA Example 3 B B Example 4 B B Example 5 B B Example 6 B C Example 7 B CExample 8 A A Example 9 A A Example 10 B B Example 11 B B Example 12 B BExample 13 B C Example 14 B C Comparative Example 1 E D ComparativeExample 2 E D Comparative Example 3 E D Comparative Example 4 E D

As apparent from Table 2, according to the invention, athree-dimensional shaped article having excellent mechanical strengthand excellent dimensional accuracy could be obtained. On the other hand,in Comparative Examples, satisfactory results were not obtained.

What is claimed is:
 1. A composition, comprising: a cellulose derivativehaving a liquid crystalline functional group; and a liquid crystallinesolvent having a reactive functional group.
 2. The composition accordingto claim 1, wherein the reactive functional group contains acarbon-carbon double bond.
 3. The composition according to claim 2,wherein the reactive functional group is a (meth)acryloyl group.
 4. Thecomposition according to claim 1, wherein the cellulose derivative hasthe liquid crystalline functional group introduced into a repeating unitof a polymer chain having a repeating structure introduced into acellulose backbone structure.
 5. The composition according to claim 1,wherein the cellulose derivative contains an ionic moiety as a chemicalstructure in common with an ionic liquid.
 6. The composition accordingto claim 5, wherein the cellulose derivative has a block containing aplurality of ionic moieties and a block containing a plurality of liquidcrystalline functional groups.
 7. The composition according to claim 1,wherein a chemical reaction involving the reactive functional group ofthe liquid crystalline solvent proceeds by UV irradiation.
 8. A shapedarticle production method, comprising: supplying the compositionaccording to claim 1; and allowing a chemical reaction involving thereactive functional group of the liquid crystalline solvent to proceed.9. A shaped article production method, comprising: supplying thecomposition according to claim 2; and allowing a chemical reactioninvolving the reactive functional group of the liquid crystallinesolvent to proceed.
 10. A shaped article production method, which is amethod for producing a three-dimensional shaped article by performing alayer forming step of forming a layer using a composition a plurality oftimes and stacking the layers, comprising: applying the compositionaccording to claim 1 to a region where the three-dimensional shapedarticle is to be formed; and allowing a chemical reaction involving thereactive functional group of the liquid crystalline solvent to proceed.11. A shaped article production method, which is a method for producinga three-dimensional shaped article by performing a layer forming step offorming a layer using a composition a plurality of times and stackingthe layers, comprising: applying the composition according to claim 2 toa region where the three-dimensional shaped article is to be formed; andallowing a chemical reaction involving the reactive functional group ofthe liquid crystalline solvent to proceed.
 12. The shaped articleproduction method according to claim 10, wherein the application of thecomposition is performed by an inkjet method.
 13. The shaped articleproduction method according to claim 10, wherein when the composition isapplied to a region where the three-dimensional shaped article is to beformed, the cellulose derivative is in a dissolved state in the liquidcrystalline solvent in the composition.
 14. The shaped articleproduction method according to claim 8, wherein the composition isapplied onto a member having been subjected to an alignment treatment.15. A shaped article, which is produced using the composition accordingto claim
 1. 16. A shaped article, which is produced using thecomposition according to claim
 2. 17. A shaped article, which isproduced using the production method according to claim
 8. 18. A shapedarticle, which is produced using the production method according toclaim
 10. 19. The shaped article according to claim 15, wherein theshaped article is a stent.
 20. The shaped article according to claim 17,wherein the shaped article is a stent.